KR20070088986A - Red electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

Provided are a novel red light emitting organic compound which is improved in electroluminescent efficiency and lifetime, and an organic light emitting device containing the compound. A red light emitting organic compound is represented by the formula(1), wherein L is an organic ligand; R1 to R10 are independently H, a halogen atom, a linear or branched C1-C20 alkyl or alkoxy group, a C6-C20 aryl group substituted or unsubstituted with a C1-C20 alkyl group, a C5-C20 hetero ring or heteroaryl group, a ketone group, a C1-C20 alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, or a dicyanoethylene group, or are connected with an adjacent substituent by a C2-C10 alkylene containing or not containing a fused ring to form an alkyl ring or a fused ring; R11 to R12 are independently a linear or branched C1-C12 alkyl group, a C5-C10 cycloalkyl group, a C6-C10 aromatic group substituted or unsubstituted with a C1-C20 alkyl group, or a C6-C20 hetero ring or hetero aromatic ring; and n is 1-3.

Description

Red electroluminescent compounds and organic electroluminescent device using the same}

1 is a cross-sectional view of an OLED,

2 is an EL spectrum of an OLED adopting pqF-2 and pqF-17, which are red phosphorescent compounds according to the present invention,

3 is a current density-voltage characteristic of an OLED adopting pqF-2 and pqF-17, which are red phosphorescent compounds according to the present invention,

4 is a luminance-driven voltage characteristic of an OLED adopting pqF-2 and pqF-17, which are red phosphorescent compounds according to the present invention,

5 is a light emission efficiency-luminance characteristics of OLEDs employing pqF-2 and pqF-17, which are red phosphorescent compounds, according to the present invention.

* Detailed description of the main symbols in the drawings *

1-Glass for organic EL 2-ITO thin film for transparent electrode

3-hole transport layer 4-light emitting layer

5-hole blocking layer 6-electron transport layer

7-electron injection layer 8-cathode

The most important factor in determining the luminous efficiency in OLED is the light emitting material. Fluorescent materials are widely used as the light emitting materials to date, but the development of phosphorescent materials is one of the best ways to improve the luminous efficiency up to four times in theory.

To date, the iridium (III) complexes are widely known as phosphorescent materials, and materials such as (acac) Ir (btp) ₂ , Ir (ppy) ₃ and Firpic are known for each RGB. In particular, many phosphorescent materials have recently been studied in Japan and Europe.

Among the conventional red phosphorescent materials, some have been reported as materials showing good EL properties, but only a few have reached the level of commercialization. The best material is an iridium complex of 1-phenyl isoquinoline, which is known to show excellent color characteristics and high luminous efficiency due to its excellent EL properties. (Ref. A. Tsuboyama, et. Al. , J Am. Chem. Soc . 2003 , 125 (42), 12971-12979)

Moreover, in the case of the red material, there is no big problem in lifespan, and if it is excellent in color purity and luminous efficiency, it tends to be commercially easy. Therefore, the iridium complex can be said to be a material having a high possibility of commercialization due to its excellent color purity and luminous efficiency.

However, the iridium complex is still judged to be a material applicable to a small display or the like, and in fact, the EL characteristic level required for medium and large OLED panels has a problem that should be superior to known materials.

Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide a compound having a skeleton of superior properties than the existing red phosphorescent material, and another object of the present invention is a medium to large OLED panel It is to provide a new light emitting compound applicable to the.

The present inventors have made an effort to solve the above-mentioned conventional problems, and have therefore invented a new red phosphorescent compound for realizing an organic EL device having excellent luminous efficiency and a markedly improved lifetime.

Accordingly, the present invention relates to a new red light emitting compound and an electroluminescent device employing the light emitting compound in the light emitting layer, and in detail, the red light emitting compound according to the present invention is characterized in that the compound of Formula 1.

[Formula 1]

L is an organic ligand;

R ₁ to R ₁₀ are each independently hydrogen, halogen, straight-chain or branched-chain alkyl group of the alkyl group, C _{1 -20} alkoxy group, C _{6 -20} aryl, C _{1 -20} for the substituted C _{1 -20} C _{6 -20} aryl group, a heterocyclic or heteroaryl of C _{5 -20} aryl group, a ketone group, an alkyl silyl C _{1 -20,} arylsilyl, alkylaryl silyl, dicyano ethylene group or, with an adjacent substituent C _{2 -} connected to alkylene of C _{2 -10} that contain a ₁₀ alkylene or a fused ring to form an alkyl ring, or a fused ring, an alkyl which is formed by an alkyl group, an alkoxy group, an aryl group and an alkylene of the C _2-20 The ring or fused ring may be substituted with one or more halogen or phenyl groups;

R ₁₁ and R ₁₂ are independently straight or branched chain alkyl group of C _{1 -12,} C _{5 -10} of the cycloalkyl group, C _{6 -10} aromatic ring, C _{1 -20} alkyl group is substituted with a C _{6 -20} of one another An aromatic ring or a C _6-20 hetero ring or hetero aromatic ring;

n is 1 to 3.

R ₁ to R ₁₀ are each independently hydrogen, fluorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, methoxy, ethoxy, butoxy, phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, naphthacenyl, 2-methylphenyl, 4- Methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2-t-butylphenyl, 2-methylnaphthyl, 4-methylnaphthyl, furan, pyridine, pyrrole, thiophene, trimethylsilyl, tripropylsilyl, tri (t -butyl) silyl, t- butyldimethylsilyl, triphenylsilyl, phenyl-dimethylsilyl, dicyano ethylene, or, is connected to an adjacent substituent via alkylene of C _{2 -4} form a cycloalkyl ring of 5-to 7-membered, or and adjacent substituents and are connected to alkylene of C _{2 -4} containing a fused ring to form a fused ring, wherein the alkyl group of C _{2 -20,} alkoxy groups, aryl groups and alkyl ring formed by an alkylene Or the fused ring may be substituted with one or more halogen or phenyl groups;

R ₁₁ and R ₁₂ independently of one another are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-amyl, n-hexyl, n-heptyl, n -Octyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 4-methylphenyl, ethylphenyl, methylnaphthyl, ethylnaphthyl Tetrahydrothiophene, tetrahydrofuran, pyrrolidine, furan, pyridine, pyrrole or thiophene;

n is 1 to 3.

In Formula 1, the compound in [] acts as a main ligand of iridium, L acts as a secondary ligand, and the organic light emitting compound according to the present invention has a tris configuration in which n = 3 without the secondary ligand L In addition to -chelated) complexes, complexes with a juligand: auxiliary ligand of 2: 1 with n = 2 are also included.

Ligand L of Formula 1 includes a structure of Formula 2 below.

[Formula 2]

In the structural formula R ₂₁ and R ₂₂ are independently hydrogen, halogen is not substituted or is straight or branched chain alkyl group of straight or branched chain alkyl group of the unsubstituted C _{1 -7,} C _{1 -7} optionally substituted with each other Phenyl group or halogen; R ₂₃ to R ₂₆ independently represent hydrogen, linear or branched alkyl group of C _{1 -7,} C _{1 - 7} alkyl silyl group, or a halogen; R ₂₇ is a phenyl group or a halogen are straight or branched chain alkyl group or straight or branched chain alkyl group of C _{1 -7} of a C _{1 -7} which is optionally substituted.

The auxiliary ligand L contained in the organic light emitting compound according to the present invention is exemplified by the following structure.

Specific examples of the compound of Formula 1, R ₁ to R ₁₀ are independently of each other hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, fluoro, trimethylsilyl, tripropylsilyl, Tri (t-butyl) silyl, t-butyldimethylsilyl, triphenylsilyl, phenyldimethylsilyl or phenyl, R ₁₀ and R ₁₁ are independently of each other methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl.

The method for preparing the iridium complex compound according to the present invention will be described based on Reaction Schemes 1 to 3 below.

Scheme 1

Scheme 2

Scheme 3

Reaction Scheme 1 is a case where n = 1 of the compound of Formula 1, iridium trichloride (IrCl ₃ ) and the secondary ligand L compound of the formula (2) in a ratio of 1: 2 to 3 molar mixture and refluxed to diiridium Remove the dimer. The solvent in the reaction step is preferably an alcohol or an alcohol / water mixed solvent, and examples thereof include 2-ethoxyethanol and 2-ethoxyethanol / water mixed solvent. The separated diiridium dimer is mixed with a compound of Formula 1, which is a main ligand, in an organic solvent and heated to prepare an organic light emitting iridium compound having a main ligand: auxiliary ligand of 1: 2 as a final product. At this time, AgCF ₃ SO ₃ , Na ₂ CO ₃ , NaOH and the like are mixed with the organic solvent 2-ethoxyethanol, 2-methoxyethyl ether and reacted.

Reaction Scheme 2 is a case where n = 2 of the compound of Formula 1, iridium trichloride (IrCl ₃ ) and zuri gande mixture of the compound of Formula 1 in the solvent in a ratio of 1: 2 to 3 mol to reflux and then diiridium dimer Disconnect. The solvent in the reaction step is preferably an alcohol or an alcohol / water mixed solvent, and examples thereof include 2-ethoxyethanol and 2-ethoxyethanol / water mixed solvent. The separated diiridium dimer is mixed with a compound of Formula 2, which is an auxiliary ligand L, in an organic solvent and heated to prepare an organic light emitting iridium compound having a ligand: auxiliary ligand of 2: 1 as a final product. Compound of Formula 1, which is a ligand of the final product The ligand and the auxiliary ligand L may be used by appropriately determining the molar ratio of reacting according to the composition ratio.In this case, AgCF ₃ SO ₃ , Na ₂ CO ₃ , NaOH, etc. may be used as the organic solvent 2-ethoxyethanol, 2-methoxyethyl ether, 1, It is reacted by mixing together in 2-dichloroethane.

Scheme 3 is the case of n = 3 of the compound of Formula 1, the iridium complex prepared in Scheme 2 and the compound of Formula 1 used as the main ligand in a ratio of 1: 2 to 3 mol to reflux by mixing An organic light-emitting iridium complex having three ligand coordinates is prepared.

Compound of formula (I) used as the main ligand in the present invention can be prepared by the following scheme 4 based on known methods.

Scheme 4

Compounds of formula (I) having various substituents can be prepared with 2-halogen quinoline derivatives and from fluorenyl boronic acid derivatives.

The compound structure of Formula 1 prepared according to the above scheme is as follows.

Hereinafter, the production method of the novel organic light emitting compound according to the present invention based on the present invention is illustrated. However, the following examples are provided to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1 Preparation of pqF-1 (Compound 116)

Preparation of Compound 112

5.0 g (20.0 mmol) of 2-bromofluorene (Compound 111) and 9.2 g (0.16 mol) of potassium hydroxide were added to 80 mL of dimethyl sulfoxide (DMSO), and 12 mL of distilled water was added dropwise thereto, followed by reaction. To the mixture was slowly added 11 g (81.5 mmol) of iodomethane (methyl iodide) and stirred at 25 ° C. for 12 hours. After stirring, 100 mL of distilled water was added to the reaction mixture, followed by extraction with 100 mL of dichloromethane and drying under reduced pressure to obtain 5.6 g (20.0 mmol) of Compound 112.

Preparation of Compound 113

5.6 g (20.0 mmol) of Compound 112 was added to 100 mL of THF, and 12 mL (30.7 mmol) of n-butyllithium (2.5 M in n-Hexane) was slowly added at -78 ° C, and stirred for 2 hours. 9.4 mL (41 mmol) of isopropyl borate ((i-pro) ₃ B) was slowly added dropwise to the reaction mixture, stirred for 12 hours, and 20 mL of 1 N HCl was added to terminate the reaction. After the reaction was completed, the reaction mixture was concentrated and dried under reduced pressure to obtain 3.3 g (13.7 mmol) of Compound 113.

Preparation of Compound 114

3.3 g (13.7 mmol) of compound 113 and 2.3 g (13.7 mmol) of 2-chlororquinoline were added to 50 mL of toluene and 25 mL of ethanol, 0.3 g (0.4 mmol) of PdCl ₂ (PPh ₃ ) ₂ , 25 mL of 2 M sodium carbonate was added and refluxed at 130 ° C. for 5 hours. After the reflux, the mixture was cooled to room temperature, extracted with distilled water, and dried under reduced pressure to obtain Compound 114 3 g (9.3 mmol).

Preparation of Compound 115

3 g (9.3 mmol) of compound 114 and 1.4 g (4.7 mmol) of iridium chloride (IrCl ₃ ) were added to 80 mL of a 2-ethoxyethanol: distilled water (3: 1) mixed solvent, followed by 24 hours. Reflux at 130 ° C. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to obtain 3.4 g (1.9 mmol) of compound 115.

Preparation of Compound 116

3.4 g (1.9 mmol) of Compound 115 was added to 0.38 g (3.8 mmol) of 2,4-penthanedione, and 1.0 g (9.5 mmol) of sodium carbonate was added to 2-ethoxyethanol. Put in 40 mL and heated to 90 ℃ for 4 hours. The reaction mixture was cooled to room temperature, the resulting solid precipitate was filtered, extracted with 100 mL of dichloromethane, and concentrated under reduced pressure. The concentrated residue was separated by silica gel column chromatography (n-hexane: dichloromethane = 15: 1), and then recrystallized with 5 mL of dichloromethane and 50 mL of n-hexane mixed solvent to obtain pqF- of the title compound as a dark red solid. 2.5 g (2.7 mmol, total yield 30%) of 1 (Compound 116) were obtained.

mp. > 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 ( m, 8H), 6.1 (s, 1H), 2.30 (s, 3H), 1.71 (s, 3H), 1.6 (s, 12H).

MS / FAB: 931 (found), 932.15 (calculated)

Preparation Example 2 Preparation of pqF-2 (Compound 117)

1 g (1 mmol) of pqF-1 (Compound 116) prepared in Preparation Example 1 and 943 mg (3 mmol) of Compound 114 were added to 30 mL of glycerol, and the mixture was stirred at 220 ° C. for 24 hours. After stirring, 50 mL of 1N aqueous hydrochloric acid solution was added to the reaction mixture, and the solid precipitate was filtered, extracted with 100 mL of dichloromethane, and concentrated under reduced pressure. The concentrated residue was separated by silica gel column chromatography (n-hexane: dichloromethane = 20: 1), and then recrystallized with a mixed solvent of 5 mL of dichloromethane and 50 mL of n-hexane to give pqF of the title compound as a dark red solid. 0.1 g (0.87 mmol, 30% yield) of -2 (compound 117) was obtained.

mp. > 320 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, H), 8.0-7.95 (m, 2H), 7.81-7.71 (m, 2H), 7.65-7.61 (m, 2H), 7.55 (d, 1H), 7.44-7.42 (m, 2H) , 7.35-7.30 (m, 2H), 1.6 (s, 6H).

MS / FAB: 1154.4 (found), 1154.4 (calculated)

Preparation Example 3 Preparation of pqF-3 (Compound 118)

0.5 g (0.28 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1 and 2,2,6,6-tetramethyl-3,5-heptanedione (2,2,6,6-tetramethyl-3 , 5-heptanedione) 0.12 mL (0.59 mmol) and 0.12 g (1.1 mmol) of sodium carbonate were added to 5 mL of 2-ethoxyethanol, and the mixture was stirred under reflux for 6 hours, and then the reaction mixture was cooled to room temperature. The solid precipitate was filtered, extracted with 100 mL of dichloromethane, and concentrated under reduced pressure. The concentrated residue was separated by silica gel column chromatography (n-hexane: dichloromethane = 20: 1), and then recrystallized with a mixed solvent of 5 mL of dichloromethane and 50 mL of n-hexane to give pqF of the title compound as a dark red solid. 29 mg (0.03 mmol, yield 13%) of -3 (compound 118) were obtained.

mp. ＞ 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 (m, 8H), 6.1 (s, 1H), 1.6 (s, 12H), 1.19 (s, 18H).

MS / FAB: 1014.4 (found), 1016.3 (calculated)

Preparation Example 4 Preparation of pqF-4 (Compound 119)

0.5 g (0.28 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1 and 1,1,1,5,5,5-hexafluoropentane-2,4-dione (1,1,1, 5,5,5-hexafluoropentane-2,4-dione) was added to 0.084 mL (0.594 mmol), sodium carbonate 0.12 g (1.13 mmol), and 5 mL of 2-ethoxyethanol at reflux at 90 ° C. for 6 hours. After stirring, the reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered, extracted with 20 mL of dichloromethane, and concentrated under reduced pressure. The concentrated residue was separated by silica gel column chromatography (n-hexane: dichloromethane = 15: 1), and then recrystallized with a mixed solvent of 5 mL of dichloromethane and 40 mL of n-hexane to give the title compound as a dark red solid. 22 mg (0.02 mmol, yield 5.1%) of pqF-4 (Compound 119) were obtained.

mp. > 290 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 (m, 8H), 6.1 (s, 1H), 1.6 (s, 12H).

MS / FAB: 1041.2 (found), 1040.08 (calculated)

Preparation Example 5 Preparation of pqF-5 (Compound 120)

0.5 g (0.28 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1 and 133 mg of 1,3-diphenylpropane-1,3-dione (1,3-diphenylpropane-1,3-dione) 0.59 mmol) and 0.12 g (1.13 mmol) of sodium carbonate were added to 5 mL of 2-ethoxyethanol, and the mixture was stirred under reflux for 6 hours. After cooling the reaction mixture to room temperature, the resulting solid precipitate was filtered and dichloromethane was used. Extracted to 20 mL, concentrated under reduced pressure. The concentrated residue was separated by silica gel column chromatography (n-hexane: dichloromethane = 18: 1), and then recrystallized with a mixed solvent of 5 mL of dichloromethane and 40 mL of n-hexane to give pqF of the title compound as a dark red solid. 31 mg (0.03 mmol, 7% yield) of −5 (compound 120) were obtained.

mp. > 310 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, 2H), 8.01- 7.95 (m, 4H), 7.84- 7.81 (m, 4H), 7.71-7.68 (m, 4H), 7.61 ( m, 2H), 7.55-7.53 (m, 3H), 7.44-7.36 (m, 8H), 7.29-7.27 (m, 4H), 7.2-7.16 (m, 3H), 6.3 (s, 1H), 1.6 ( s, 6 H)

MS / FAB: 1057.3 (found), 1056.28 (calculated)

Preparation Example 6 Preparation of pqF-6 (Compound 121)

0.3 g (0.17 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1, 40 mg (0.351 mmol) of 3-methylpentane-2,4-dione, sodium carbonate 72 mg (0.68 mmol) was added to 5 mL of 2-ethoxyethanol, and the mixture was stirred under reflux at 90 ° C. for 6 hours. The reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered and then 20 mL of dichloromethane. Extracted with. The extracted organic solution was concentrated under reduced pressure, the product was separated by silica gel column chromatography (n-hexane: dichloromethane = 10: 1), and then recrystallized with 5 mL of dichloromethane and 40 mL of n-hexane mixed solvent to obtain the title compound. 20 mg (0.021 mmol, yield 6.2%) of pqF-6 (Compound 121) of a phosphorus dark red solid was obtained.

mp. > 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 (m, 8H), 2.3 (s, 3H), 1.9 (s, 3H), 1.7 (s, 3H), 1.6 (s, 12H).

MS / FAB: 947.3 (found), 946.16 (calculated)

Preparation Example 7 Preparation of pqF-7 (Compound 122)

0.3 g (0.17 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1, 45 mg (0.351 mmol) of 3-ethylpentane-2,4-dione, sodium carbonate 72 mg (0.68 mmol) was added to 5 mL of 2-ethoxyethanol and stirred under reflux at 90 ° C. for 6 hours. After stirring was complete, the resulting solid precipitate was filtered and extracted with 20 mL of dichloromethane. The extracted organic solution was concentrated under reduced pressure to separate the product by silica gel column chromatography (n-hexane: dichloromethane = 10: 1), and then recrystallized with 5 mL of dichloromethane and 40 mL of n-hexane mixed solvent to obtain the title compound. 20 mg (0.02 mmol, 14% yield) of pqF-7 (compound 122) was obtained as a dark red solid.

mp. > 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 (m, 8H), 2.3 (s, 3H), 2.1 (q, 2H), 1.7 (s, 3H), 1.6 (s, 12H), 1 (t, 3H).

MS / FAB: 961.3 (found), 960.19 (calculated)

Preparation Example 8 Preparation of pqF-8 (Compound 127)

Preparation of Compound 123

10 g (40.8 mmol) of 2-Bromofluorene, a compound 111, was dissolved in 100 mL of diethyl ether and then n-butyllithium (n-BuLi, 2.5M in n-Hexane) at -78 ° C. 40.8 mL (102 mmol) was slowly added dropwise and stirred for 2 hours, and 16 g (143 mol) of bromoethane was slowly added thereto, followed by stirring for 12 hours while maintaining the temperature at 25 ° C. After the reaction was completed, 200 mL of distilled water was added thereto, extracted with 200 mL of dichloromethane, and dried under reduced pressure. The product was separated by silica gel column chromatography (n-hexane: dichloromethane = 20: 1), and dried to obtain 9.8 g of Compound 123. .

Preparation of Compound 124

9.8 g (32.5 mmol) of Compound 123 was added to 200 mL of THF, and 20 mL (48.8 mmol) of n-butyllithium (2.5 M in n-Hexane) was slowly added at -78 ° C, and stirred for 2 hours. 15 mL (65 mmol) of isopropyl borate ((i-pro) ₃ B) was slowly added dropwise to the reaction mixture, stirred for 12 hours, and 40 mL of 1 N HCl was added to terminate the reaction. After the reaction was completed, the reaction mixture was concentrated and dried under reduced pressure to obtain 5.2 g (19.5 mmol) of the compound 124.

Preparation of Compound 125

5.2 g (19.5 mmol) of Compound 124 and 3.5 g (21.4 mmol) of 2-chlororquinoline were added to 80 mL of toluene and 40 mL of ethanol, 0.4 g (0.6 mmol) of PdCl ₂ (PPh ₃ ) ₂ , 40 mL of 2 M sodium carbonate was added and refluxed at 130 ° C. for 5 hours. After reflux, the mixture was cooled to room temperature, extracted with distilled water, and dried under reduced pressure to obtain 5.5 g (15.6 mmol) of Compound 125.

Preparation of Compound 126

5.5 g (15.6 mmol) of Compound 125 and 2.1 g (7 mmol) of iridium chloride (IrCl ₃ ) were added to 120 mL of a 2-ethoxyethanol: distilled water (3: 1) mixed solvent, followed by 24 hours. Reflux at 130 ° C. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to obtain 4.8 g (2.6 mmol) of Compound 126.

Preparation of Compound 127

Compound 126 1 g (0.56 mmol), 2-phenylpyridine 0.26 g (1.7 mmol), AgCF ₃ SO ₃ obtained by the same method as the preparation method of Compound 113, Compound 114, and Compound 115 of Preparation Example 1 0.44 g (1.7 mmol) and 20 mL of 2-methoxyethylether were used to obtain 90.2 mg (0.02 mmol, total yield 18%) of the title compound pqF-8 (compound 127) as a scarlet crystal. .

mp. > 300 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.3 (s, 2H), 8.0-7.95 (m, 5H), 7.85 (d, J = 8 Hz, 2H), 7.7-7.68 (m, 4H), 7.6-7.55 (m, 5H), 7.46-7.4 (m, 5H), 7.35-7.28 (m, 7H), 6.8 (t, J = 6.5 Hz, 1H), 1.9 (q, 4H), 0.9 (t, 6H).

MS / FAB: 1041.4 (found), 1043.32 (calculated)

Preparation Example 9 Preparation of pqF-9 (Compound 131)

Preparation of Compound 130

1 g (6.3 mmol) of 2-Bromopyridine, Compound 128, 1.1 g (6.9 mmol) of 4-tert-butylphenylboronic acid, Compound 129, toluene 30 mL), ethanol (15 mL), 2M sodium carbonate (15 mL) and PdCl ₂ (PPh ₃ ) _{2 using} 0.13 g (0.19 mmol) in the same manner as in the preparation of Compound 114 of Preparation Example 1 0.93 g (4.41 mmol) was obtained.

Preparation of Compound 131

1 g (0.56 mmol) of Compound 126, 189 mg (1.08 mmol) of Compound 128, 0.28 g (1.08 mmol) of AgCF ₃ SO ₃ , and 15 mL of 2-methoxyethylether were used to prepare Compound 8 and In the same manner, 90.2 mg (0.2 mmol, yield 3%) of the title compound iridium complex pqF-9 (compound 131) were obtained.

mp. > 300 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.3 (s, 2H), 8.0-7.95 (m, 5H), 7.85 (d, J = 8 Hz, 2H), 7.7-7.68 (m, 4H), 7.6-7.55 (m, 5H), 7.46-7.42 (m, 5H), 7.36-7.28 (m, 6H), 6.8 (t, J = 6.5 Hz, 1H), 1.9 (q, 4H), 1.4 (s, 9H), 0.9 (t, 6H).

MS / FAB: 1100.4 (found), 1099.43 (calculated)

Preparation Example 10 Preparation of pqF-10 (Compound 133)

0.3 g (0.16 mmol) of the dichlorodiiridium compound 126 prepared in Preparation Example 8, 70 mg (0.49 mmol) of 2-Pyrrole-pyridine, which is Compound 132, and 1.2-dichloroethane (1,2- 10 mL of dichloroethane) was used to obtain 80 mg (0.08 mmol, 23% yield) of the title compound iridium complex pqF-10 (compound 133) in the same manner as in Preparation Example 8.

mp. > 290 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.66 (d, J = 8.5 Hz, 1H), 8.3 (s, 2H), 8.0 (s, 2H), 7.92 (d, 2H), 7.83-7.81 (m, 3H), 7.7-7.68 (m, 4H ), 7.6-7.55 (m, 5H), 7.42-7.4 (m, 4H), 7.36-7.28 (m, 5H), 6.5 (d, J = 6.0 Hz, 1H), 6 (m, 2H), 1.9 ( q, 4H), 0.9 (t, 6H).

MS / FAB: 1030.4 (found), 1032.3 (calculated)

Preparation Example 11 Preparation of pqF-11 (Compound 135)

0.3 g (0.16 mmol) of the dichlorodiiridium compound 126 prepared in Preparation Example 8, 70 mg (0.49 mmol) of 2-imidazole-pyridine, which is Compound 134, and 1.2-dichloroethane (1,2) 10 mg of -dichloroethane) was obtained in the same manner as in Preparation Example 8, to obtain 80 mg (0.08 mmol, yield 22%) of the title compound iridium complex pqF-11 (compound 135).

mp. > 290 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.66 (d, J = 8.5 Hz, 1H), 8.3 (s, 2H), 8.0 (d, 2H), 7.92 (s, 2H), 7.83-7.81 (m, 3H), 7.7-7.68 (m, 4H ), 7.6-7.55 (m, 5H), 7.42-7.4 (m, 4H), 7.36-7.28 (m, 5H), 7.1 (m, 2H), 1.9 (q, 4H), 0.9 (t, 6H).

MS / FAB: 1031.4 (found), 1033.29 (calculated).

Preparation Example 12 Preparation of pqF-12 (Compound 143)

Preparation of Compound 137

20 g (408 mmol) of 2-Acetylfluorene (Compound 136) was dissolved in 500 mL of toluene, and 14 g (12 mmol) of trimethylaluminum (AlMe ₃ ) was added thereto, and the mixture was stirred under reflux for 10 hours. After the reaction was cooled to room temperature, 200 mL of cold 1N hydrochloric acid solution was slowly added. 200 mL of distilled water was added to the reaction solution, and the mixture was extracted with 200 mL of dichloromethane, concentrated under reduced pressure, separated by silica gel column chromatography (n-hexane: dichloromethane = 15: 1), and then dried to obtain Compound 137 12 g (54 mmol). Got it.

Preparation of Compound 138

12 g (54 mmol) of Compound 137 was dissolved in 300 mL of diethyl ether, and 54 mL (135 mmol) of n-butyllithium (n-BuLi, 2.5 M in n-Hexane) was slowly added at -78 ° C, and -78 ° C. Stir for 2 hours while maintaining. 36.5 g (189 mol) of n-bromooctane was slowly added dropwise to the reaction mixture, which was stirred for 12 hours while maintaining the temperature at 25 ° C. 50 mL of distilled water was added to the reaction mixture, followed by extraction with 300 mL of chloroform and concentration under reduced pressure. The product was separated by silica gel column chromatography (n-hexane: dichloromethane = 12: 1) to obtain 21 g (47 mmol) of Compound 138.

Preparation of Compound 139

21 g (47 mmol) of compound 138 was dissolved in 500 mL of dichloromethane, and 8.26 g (51.7 mmol) of bromine was slowly added dropwise at 0 ° C, and stirred at 25 ° C for 12 hours. After stirring, 1 L of 1N Na ₂ S ₂ O ₃ aqueous solution was added to the reaction mixture, which was then extracted with ethyl acetate, dried, separated by silica gel column chromatography (n-hexane: dichloromethane = 8: 1), and dried. 20 g (38 mmol) of compound 139 were obtained.

Preparation of Compound 140

20 g (38 mmol) of Compound 139 was added 400 mL of tetrahydrofuran, and 35.6 mL (57 mmol) of n-butyllithium ( n- BuLi, 1.6 M in n-Hexane) was slowly added at -78 ° C, and -78 ° C. Stir for 2 hours while maintaining. After stirring was completed, 14.3 g (76 mmol) of isopropyl borate (i-pro ₃ B) was added and stirred for 12 hours while maintaining the temperature of 25 ℃. 100 mL of distilled water was added to the mixed reaction mixture, extracted with 200 mL of dichloromethane, and dried. 1 L of n-hexane was added thereto, and the resulting crystal was filtered under reduced pressure to obtain 12.1 g (24.7 mmol) of Compound 140.

Preparation of Compound 142

Using compound 140, Compound 142 2 g (0.7 mmol) was obtained by the same method as the method for preparing compound 114 and compound 115 of Preparation Example 1.

Preparation of Compound 143

2 g (0.7 mmol) of compound 142 and 355 mg (2.1 mmol) of 2-p-tolylpyridine, 540 mg (2.1 mmol) of AgCF ₃ SO ₃ , 2-methoxyethylether In the same manner as in Preparation Example 10, using 20 mL to obtain 0.32 g (0.2 mmol, yield 3%) of the title compound red crystals of the iridium complex pqF-12 (Compound 143).

mp. > 340 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.28 (s, 2H), 8-7.94 (m, 4H), 7.86-7.84 (m, 3H), 7.71-7.67 (m, 4H), 7.6-7.56 (m, 5H), 7.46-7.43 (m, 5H), 7.38 (d, 2H), 7.1-6.99 (m, 3H), 3.3 (s, 8H), 2.38 (S, 3H), 1.8 (S, 8H ), 1.33-1.30 (m, 58H), 1 (S, 12H).

MS / FAB: 1506.9 (found), 1506.2 (calculated).

Preparation Example 13 Preparation of pqF-13 (Compound 146)

Preparation of Compound 145

1 g (6.3 mmol) of 2-Bromopyridine, Compound 128, 0.97 g (6.9 mmol) of 4-fluorophenylboronic acid, Compound 144, 30 mL of toluene, 15 mL of ethanol , Compound 145 in the same manner as in the preparation of Compound 114 of Preparation Example 1 using 2M aqueous sodium hydroxide solution (15 mL) and 0.13 g (0.19 mmol) of PdCl ₂ (PPh ₃ ) _2. 0.98 g (5.65 mmol) was obtained.

Preparation of Compound 146

1 g (0.36 mmol) of the dichlorodiiridium compound 142 prepared in Preparation Example 12, 189 mg (1.08 mmol) of the compound 145, 0.277 g (1.08 mol) of AgCF ₃ SO ₃ , and 2-methoxyethylether (2-methoxyethylether) Using 15 mL to obtain 0.4 g (0.3 mmol, yield 4%) of the title compound iridium complex pqF-13 (Compound 146) in the same manner as in Preparation Example 10.

mp. > 340 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.28 (s, 2H), 8-7.94 (m, 4H), 7.86-7.84 (m, 3H), 7.71-7.67 (m, 4H), 7.6-7.56 (m, 5H), 7.46-7.43 (m, 5H), 7.38 (d, 2H), 7.1-6.99 (m, 3H), 3.3 (s, 8H), 1.8 (S, 8H), 1.33-1.30 (m , 58H), 1 (S, 12H).

MS / FAB: 1508.9 (found), 1510.17 (calculated).

Preparation Example 14 Preparation of pqF-14 (Compound 148)

Preparation of Compound 147

5 g (31.8 mmol) of bromobenzene was dissolved in 20 mL of diethyl ether, and then slowly added 15.3 mL (38.2 mmol) of n-butyllithium (n-BuLi, 2.5 M in n-Hexane) at -78 ° C. After stirring at 25 ° C. for 2 hours. After drying the diethyl ether used in the reaction under reduced pressure, 4.3 g (31.8 mmol) of 4-tert-Buthylpyridine dissolved in 20 mL toluene were added to the reaction, followed by reflux at 130 ° C. for 12 hours. Stirred. After stirring, 250 mL of distilled water was slowly added to the reaction mixture, washed with 200 mL of brine, extracted with 200 mL of diethyl ether, and dried under reduced pressure, followed by silica gel column chromatography (n-hexane: dichloromethane = 16: 1). 2 g (9.46 mmol) of Compound 147 was obtained.

Preparation of Compound 148

1 g (0.36 mmol) of the dichlorodiiridium compound 142 prepared in Preparation Example 12, 189 mg (1.08 mmol) of the compound 147, 0.28 g (1.08 mmol) of AgCF ₃ SO ₃ , and 2-methoxyethylether (2-methoxyethylether) (15 mL) was used in the same manner as in Preparation Example 10, to obtain 0.32 g (0025 mmol, Yield 4%) of the title compound Red Crystalline Iridium Complex pqF-14 (Compound 148).

mp. > 340 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.28 (s, 2H), 8-7.94 (m, 4H), 7.86-7.84 (m, 3H), 7.71-7.67 (m, 4H), 7.6-7.56 (m, 5H), 7.46-7.43 (m, 5H), 7.38 (d, 2H), 7.1-6.99 (m, 3H), 3.3 (s, 8H), 2.38 (S, 3H), 1.8 (S, 8H ), 1.33-1.30 (m, 58H), 1.01 (S, 12H).

MS / FAB: 1504.9 (found), 1506.2 (calculated).

Preparation Example 15 Preparation of pqF-15 (Compound 150)

0.3 g (0.12 mmol) of the dichlorodiiridium compound 142 prepared in Preparation Example 12 and 43 mg (0.374 mmol) of the 2- (pyridinyl) benzoimidazole which is the compound 149 (0.374 mmol) and 1.2-dichloroethane Using 10 mL of (1,2-dichloroethan), 29 mg (0.02 mmol, yield 13%) of the title compound iridium complex pqF-15 (compound 150) were obtained in the same manner as in Preparation Example 10.

mp. > 340 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.56 (d, J = 8.5 Hz, 1H), 8.28 (s, 2H), 8-7.94 (m, 4H), 7.84-7.81 (m, 3H), 7.73-7.7 (m, 6H), 7.6-7.56 (m, 5H), 7.42-7.39 (m, 6H), 7.3-7.28 (m, 3H), 3.3 (s, 8H), 1.8 (S, 8H), 1.33-1.30 (m, 58H), 1 (S , 12H).

MS / FAB: 1531.9 (found), 1532.3 (calculated).

Preparation Example 16 Preparation of pqF-16 (Compound 152)

0.3 g (0.12 mmol) of the dichlorodiiridium compound 142 prepared in Preparation Example 12, 43 mg (0.37 mmol) of picolinic acid (compound 151), and 10 mL of 1.2-dichloroethane (1,2-dichloroethan) In the same manner as in Preparation Example 8, 29 mg (0.02 mmol, 13% yield) of the title compound iridium complex pqF-16 (compound 152) was obtained.

mp. > 340 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 9 (d, 1H), 8.33-8.28 (m, 3H), 8.15 (t, 1H), 8-7.94 (m, 4H), 7.85-7.84 (m, 3H), 7.73-7.7 (m, 4H) , 7.6-7.56 (m, 4H), 7.42-7.39 (m, 6H), 3.3 (s, 8H), 1.8 (S, 8H), 1.33-1.30 (m, 58H), 1 (S, 12H).

MS / FAB: 1456.8 (found), 1460.09 (calculated).

Preparation Example 17 Preparation of pqF-17 (Compound 160)

Preparation of Compound 154

60 g (185.1 mmol) of compound 153, 2,7-dibromofluorene, 83.1 g (1.1 mol) of potassium hydroxide, 750 mL of dimethyl sulfoxide (DMSO), 135 mL of distilled water, and iodo Using 62 g (433.8 mmol) of methane, 58.8 g (166.8 mmol) of Compound 154 were obtained by the same method as the compound 112 of Preparation Example 1.

Preparation of Compound 155

Compound 154 50.0 g (142 mmol) of tetrahydrofuran into a 87 mL, at -78 ℃ n - slowly added butyllithium (n-BuLi, 1.6 M in n-Hexane) to 89 mL (142 mmol) for 30 min. 18.5 g (170.5 mmol) of chlorotrimethylsilane (TMSCl) were added slowly and stirred at 25 ° C. for 12 hours. 100 mL of distilled water was added to the reaction mixture, followed by extraction with 200 mL of diethyl ether. Then, 200 mL of dichloromethane was added thereto, and the precipitate was filtered under reduced pressure to give 25.0 g (72.4 mmol) of Compound 155 under reduced pressure.

Preparation of Compound 156

Compound 155 18 g (52.1 mmol), tetrahydrofuran 350 mL, n - butyl lithium (n-BuLi, 1.6 M in n-Hexane) 32.6 mL (52.1 mmol) and isopropyl borate _{((i-pro) 3 B} ) Compound 156 in the same manner as in Preparation Example 1, using 19.6 g (104.4 mmol) 15.5 g (50.0 mmol) was obtained.

Preparation of Compound 157

Compound 156 15.5 g (50.0 mmol), 2-chloroquinoline 9.8 g (60 mmol), 200 mL toluene, 100 mL ethanol, 100 mL 2M sodium carbonate and 1.75 g PdCl ₂ (PPh ₃ ) ₂ 2.5 mmol) was used to obtain Compound 1157 g (45.0 mmol) in the same manner as in Preparation Example 1.

Preparation of Compound 159

30 g (193 mmol) of 2-Phenylpyridine, Compound 158, 10.7 g (88 mmol) of iridium chloride (IrCl ₃ ), 450 mL of 2-ethoxyethanol and 150 mL of distilled water Compound 159 35 g (32.6 mmol) was obtained in the same manner as in Preparation Example 1 above.

Preparation of Compound 160

16.1 g (15 mmol) of Compound 159, 17.7 g (45.0 mmol) of Compound 157, AgCF ₃ SO ₃ 11.6 g (45.0 mmol) and 240 mL of 2-methoxyethylether (Preparation Example) In the same manner as in 1, 15.2 g (17 mmol, 9% yield) of the title compound, iridium complex pqF-17 (compound 160), which was a scarlet crystal, was obtained.

mp. > 300 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.56 (d, 2H), 8.1-8 (m, 3H), 7.8 (s, 2H), 7.7 (d, 2H), 7.6 (d, 2H), 745-7.42 (m, 3H), 7.33-7.3 (m, 6H), 6.96 (m, 2H), 1.67 (s, 6H), 0.55 (s, 9H).

MS / FAB: 894.3 (found), 893.18 (calculated).

Preparation Example 18 Preparation of pqF-18 (Compound 167)

Preparation of Compound 162

50 g (204 mmole), 2-bromofluorene, Compound 161, 68.7 g (1224 mmol) of potassium hydroxide, 850 mL of dimethylsulfoxide (DMSO), 150 mL of distilled water and 12.4 g (87) of iodomethane mmol) to give 51.9 g (190 mmol) of the compound 162 in the same manner as in Preparation Example 1.

Preparation of Compound 163

51.9 g (190 mmol) compound 162, 700 mL tetrahydrofuran, 118.8 mL (190 mmol) and isopropylborate ((i-pro) ₃ B) 71.2 n -butyllithium ( n- BuLi, 1.6 M in hexane) 71.2 39.3 g (165 mmol) of Compound 163 were obtained by the same method as Preparation Example 1 using g (380 mmol).

Preparation of Compound 164

39.3 g (165 mmol) of compound 163 and 29.7 g (181.5 mmol) of 2-chloroquinolin, 600 mL of toluene, 300 mL of ethanol, 300 mL of 2 M sodium carbonate, 5.8 g of PdCl ₂ (PPh ₃ ) ₂ (8.25 mmol) was used to obtain 48.9 g (152 mmol) of Compound 164 in the same manner as in Preparation Example 1.

Preparation of Compound 166

50 g (243.9 mmol) of compound 165, 2-phenylquinoline, 32.7 g (109.8 mmol) of iridium chloride (IrCl ₃ ), 600 mL of 2-ethoxyethanol and 200 mL of distilled water were used. To obtain the compound 166 67.7 g (53.2 mmol) in the same manner as in Preparation Example 1.

Preparation of Compound 167

51 g (51 mmol) of Compound 166, 48.9 g (152 mmol) of Compound 164, 39.1 g (152 mmol) of AgCF ₃ SO ₃ and 800 mL of 2-Methoxyethylether were prepared. In the same manner as in 14, 56.2 g (61 mmol, Yield 30%) of the title compound red crystals of iridium complex pqF-18 (Compound 167) were obtained.

mp. 300〉 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 8.3 (s, 1H), 8 (m, 3H), 7.9 (s, 1H), 7.85 (d, 1H), 7.7-7.69 (m, 6H), 7.53 (d, 1H), 7.43-7.41 (m , 6H), 7.35-7.3 (m, 8H), 1.67 (s, 6H)

MS / FAB: 919.3 (found), 921.12 (calculated).

Preparation Example 19 Preparation of pqF-19 (Compound 173)

Preparation of Compound 154

60 g (185.1 mmole) of compound 153, 2,7-dibromofluorene, 83.1 g (1.1 mol) of potassium hydroxide, 750 mL of dimethylsulfoxide (DMSO), 135 mL of distilled water, and iodomethane Using 62 g (433.8 mmol) in the same manner as in Preparation Example 1, 58.8 g (166.8 mmol) of Compound 154 was obtained.

Preparation of Compound 168

Using the resulting compound 154 50.0 g (142 mmol), THF 875 mL, n- butyllithium (n -BuLi, 1.6 M in n -Hexane) 89 mL (142 mmol) and iodomethane 24.2 g (170.5 mmol) 20.8 g (72.4 mmol) of Compound 168 was obtained by the same method as in Preparation Example 1 above.

Preparation of Compound 169

20.8 g (72.4 mmol) compound 168, THF 500 mL, n-butyllithium ( n- BuLi, 1.6 M in n-Hexane) 45.3 mL (72.4 mmol) and isopropylborate ((i-pro) ₃ B) 27.2 15.4 g (61 mmol) of Compound 169 were obtained by the same method as Preparation Example 1 using g (144.8 mmol).

Preparation of Compound 170

15.4 g (61 mmol) of compound 169, 12 g (73.2 mmol) of 2-chloroquinoline, 240 mL of toluene, 120 mL of ethanol, 120 mL of 2 M sodium carbonate and 2.2 g of PdCl ₂ (PPh ₃ ) ₂ 3.1 mmol) was used to obtain 17.8 g (53.0 mmol) of compound 170 in the same manner as in Preparation Example 1.

Preparation of Compound 172

50 g (244 mmol) of 2-phenylquinoline, Compound 171, 13.5 g (111 mmol) of iridium chloride (IrCl ₃ ), 600 mL of 2-ethoxyethanol, and 200 mL of distilled water were used. To obtain 46 g (36.2 mmol) of Compound 172 in the same manner as in Preparation Example 1.

Preparation of Compound 173

22.5 g (17.7 mmol) of Compound 172, 17.8 g (53.0 mmol) of Compound 170, 13.6 g (53.0 mmol) of AgCF ₃ SO ₃ and 280 mL of 2-methoxyethylether were prepared using In the same manner, 9.4 g (10 mmol, 6% yield) of the title compound red crystals of iridium complex pqF-19 (compound 173) were obtained.

mp. > 300 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 9.2 (s, 2H), 8.3 (s, 1H), 8.1 (d, J = 8 Hz, 1H), 8.0 (d, J = 7.7 Hz, 2H), 7.9-7.88 (m, 3H), 7.72- 7.7 (m, 5H), 7.64-7.6 (m, 3H), 7.55-7.51 (m, 4H), 7.4 7.39-7.35 (m, 6H), 7.29-7.26 (m, 3H), 7.2 (d, J = 5.3 Hz, 1H), 2.35 (s, 3H), 1.64 (s, 6H).

MS / FAB: 935.3 (found), 935.14 (calculated).

Preparation Example 20 Preparation of pqF-20 (Compound 181)

Preparation of Compound 175

200 g (844.2 mmol) of 2,5-dibromopyridine, Compound 174, 113.2 g (928.6 mmol) of phenylboronic acid, 17.8 g of PdCl ₂ (PPh ₃ ) ₂ mmol), 600 mL of toluene, 300 mL of ethanol and 300 mL of 2 M sodium hydroxide were used to obtain 143 g (611 mmol) of Compound 175 in the same manner as in Preparation Example 1.

Preparation of Compound 176

Compound 175 143 g (611 mmol) of diethyl ether was added to 1.5 L dissolved in n- butyllithium (n -BuLi, 1.6 M in n -Hexane) 366.6 mL (916.5 mmol) slowly at -78 ℃ the following N, N 84.4 g (733.2 mmol) of dimethylacetamide were added and then stirred at 25 ° C. for 12 hours. 200 mL of ammonium chloride was added to the reaction mixture, which was extracted with 300 mL of ethyl acetate and dried under reduced pressure to obtain 90.1 g (400 mmol) of Compound 176.

Preparation of Compound 177

Prepared using 60 g (185.1 mmol) of 2,7-dibromofluorene compound 153, 83.1 g (1.1 mol) of potassium hydroxide, 750 mL of dimethyl sulfoxide, 135 mL of distilled water and 62 g (433.8 mmol) of iodomethane. 60.2 g (171 mmol) of compound 154 was obtained in the same manner as in Example 1. The resulting compound 154 49.3 g (140 mmol), tetrahydrofuran 875 mL, n- butyllithium (n -BuLi, 1.6 M in n -Hexane) 87.5 mL (140 mmol) and dibromoethane (bromoethane) 18.9 g (154 mmol) to give 19.7 g (65.5 mmol) of compound 177 in the same manner as in Preparation Example 1.

Preparation of Compound 178

19.7 g (65.5 mmol) compound 177, 400 mL tetrahydrofuran, 45.1 mL (72.1 mmol) n-butyllithium ( n -BuLi, 1.6 M in n-Hexane) and isopropylborate ((i-pro) ₃ B 16.8 g (63 mmol) of Compound 178 were obtained by the same method as Preparation Example 1, using 24.6 g (131 mmol).

Preparation of Compound 179

16.8 g (63 mmol) of Compound 178 and 11.9 g (72.45 mmol) of 2-chloroquinoline, 200 mL of toluene, 100 mL of ethanol, 100 mL of 2M aqueous sodium carbonate solution and 1.3 g of PdCl ₂ (PPh ₃ ) ₂ (1.89 mmol) was used to obtain 17.5 g (50 mmol) of the compound 179 in the same manner as in Preparation Example 1.

Preparation of Compound 180

17.5 g (50 mmol) of Compound 179, 2.74 g (22.5 mmol) of iridium chloride (IrCl ₃ ), 120 mL of 2-ethoxyethanol and 40 mL of distilled water in the same manner as in Preparation Example 1 14.8 g (8 mmol) of compound 180 were obtained.

Preparation of Compound 181

14.8 g (8 mmol) of Compound 180, 48.9 g (24 mmol) of Compound 176, 93.4 g (24 mmol) of AgCF ₃ SO ₃ and 120 mL of 2-methoxyethylether (Preparation Example) In the same manner as in 1, 5.8 g (5.3 mmol, Yield 3%) of the title compound Iridium complex pqF-20 (compound 181) of cerise crystals were obtained.

 mp. > 290 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 9.26 (s, 1H), 8.3 (s, 2H), 8.15 (d, J = 8.7 Hz, 1H), 8.1 (d, J = 8 Hz, 2H), 8.0 (d, J = 8.3 Hz, 1H) , 7.9 (s, 2H), 7.8-7.84 (m, 5H), 7.6-7.7 (m, 6H), 7.31-7.4 (m, 9H), 2.59-2.66 (m, 4H), 2.55 (s, 3H) , 1.67 (s, 12H), 1.24 (t, J = 3.5 Hz, 6H).

MS / FAB: 1083.4 (found), 1085.36 (calculated).

Preparation Example 21 Preparation of pqF-21 (Compound 184)

Preparation of Compound 182

200 g (844.2 mmol) of 2,5-dibromopyridine as compound 174, 165.3 g (928.6 mmol) of 4-tert-butylphenylboronic acid as compound 129 180.2 g (621 mmol) of Compound 182 was obtained by the same method as Preparation Example 1, using 17.8 g (25.3 mmol) of PdCl ₂ (PPh ₃ ) ₂ , 600 mL of toluene, 300 mL of ethanol, and 300 mL of 2M sodium carbonate.

Preparation of Compound 183

180.2 g (621 mmol) of compound 182, diethyl ether 1.8 l, n-butyllithium ( n- BuLi, 1.6 M in n-Hexane), 582.2 mL (931.5 mmol), N, N -dimethylisobutylamide ( N , N -dimethylisobutyramide) 85.8 g (745.2 mmol) was used to obtain the compound 183 108.6 g (386 mmol) in the same manner as in the preparation of the compound 176 of Preparation Example 20.

Preparation of Compound 184

34.8 g (20 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1, 16.9 g (60 mmol) of Compound 183, 15.4 g (60 mmol) of AgCF ₃ SO ₃ , and 250 mL of 2-methoxyethylether were prepared. In the same manner as in Preparation Example 1, 13.5 g (12.1 mmol, yield 6%) of the title compound red crystals of the iridium complex pqF-21 (compound 184) were obtained.

mp. > 290 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 9.28 (s, 1H), 8.3 (s, 2H), 8.15 (d, J = 8.6 Hz, 1H), 8.1 (d, J = 8 Hz, 2H), 7.8-7.9 (m, 8H), 7.7 ( d, J = 6.5 Hz, 2H), 7.58-7; .61 (m, 6H), 7.40-7.46 (m, 6H), 7.3 (dd, J = 4.5, 5.3 Hz, 2H), 2.7 (s, 1H ), 1.67 (s, 12H), 1.34 (s, 9H), 1.23 (d, 6H).

MS / FAB: 1111.42 (found), 1113.42 (calculated).

Preparation Example 22 Preparation of pqF-22 (Compound 191)

Preparation of Compound 185

Compound 174 is 2, 5-dibromo-pyridine (2,5-dibromo pyridine) 100 g (422 mmol), 4- tolyl boronic acid (r -tolylboronic acid) 63.1 g ( 464.2 mmol), PdCl 2 (PPh 3) ₂ Compound 185 in the same manner as in Preparation Example 1, using 8.9 g (12.7 mmol), 300 mL of toluene, 150 mL of ethanol, and 150 mL of 2M aqueous sodium carbonate solution 77.2 g (311 mmol) was obtained.

Preparation of Compound 186

Compound 185 of 77.2 g (311 mmol), 1 L of diethyl ether, n- butyl lithium (n -BuLi, 1.6 M in n -Hexane) 213.8 mL (342.1 mmol), 2,2- N, N - tetramethyl-propionamide 48.2 g (373.2 mmol) of amide (2,2, -N, N- tetramethylpropionamide) was used to obtain 75.5 g (298 mmol) of Compound 186 in the same manner as in Preparation Example 1.

Preparation of Compound 187

50 g (204 mmol) of 2-bromofluorene, a compound 111, and 21.9 g (68 mmol) of tetrabutylammonium bromide were suspended in 400 mL of 50% aqueous sodium hydroxide solution, and the mixture was stirred under reflux at 60 ° C. for 60 minutes. 78.8 g (408 mmol) of 1-bromooctane was added to the reaction and stirred for 12 hours. The reaction mixture was extracted with 200 mL of diethyl ether, and concentrated under reduced pressure. Then, silica gel column chromatography (n-hexane: dichloromethane = 25: 1) afforded 79.5 g (169.32 mmol) of compound 187.

Preparation of Compound 188

79.5 g (169.32 mmol) n- butyl lithium into the compound 187 in 1 L of tetrahydrofuran (n -BuLi, 1.6 M in n -Hexane) 116 mL (186.3 mmol), triisopropyl borate (Triisopropyl borate) 63.7 g (338.6 mmol) was used to obtain 65.6 g (151 mmol) of Compound 188 in the same manner as in Preparation Example 1.

Preparation of Compound 189

65.6 g (151 mmol) of Compound 188 and 29.5 g (181.2 mmol) of 2-chloroquinoline, 400 mL of toluene, 200 mL of ethanol, 200 mL of 2M aqueous sodium hydroxide solution and 5.3 g of PdCl ₂ (PPh ₃ ) ₂ (7.55 mmol) was used to obtain 68.8 g (133 mmol) of Compound 189 in the same manner as in Preparation Example 1.

Preparation of Compound 190

68.8 g (133 mmol) of Compound 189 and 18.1 g (60.52 mmol) of iridium chloride (IrCl ₃ ), 300 mL of 2-ethoxyethanol and 100 mL of distilled water were used in the same manner as in Preparation Example 1. 55.8 g (22.1 mmol) of compound 190 were obtained.

Preparation of Compound 191

55.8 g (22.1 mmol) of compound 190, 16.8 g (66.3 mmol) of compound 186, 17 g (66.3 mmol) of AgCF ₃ SO ₃ and 280 mL of 2-methoxyethylether In the same manner as in 1, 23.6 g (16 mmol, 8% yield) of an iridium complex pqF-22 (compound 191) as a title compound was obtained.

mp. > 290 ℃

¹ H NMR (300 MHz, CDCl ₃ ): δ = 9.28 (s, 1H), 8.3 (s, 2H), 8.15 (d, J = 8.6 Hz, 1H), 8.1 (d, J = 8.1 Hz, 2H), 7.8-7.9 (m, 8H), 7.7 ( d, J = 6.6 Hz, 2H), 7.55-7.6 (m, 6H), 7.3-7.4 (m, 6H), 7.18-7.2 (m, 2H), 3.3 (s, 8H), 2.35 (s, 3H) , 1.8 (s, 8H), 1.33-1.28 (m, 49H), 0.96 (s, 12H).

MS / FAB: 1477.83 (found), 1478.11 (calculated).

Preparation Example 23 Preparation of pqF-23 (Compound 197)

Preparation of Compound 192

20 g (84.4 mmol) of 2,5-dibromopyridine, Compound 174, 11.3 g (92.9 mmol) of phenylboronic acid, 1.8 g (2.5) of PdCl ₂ (PPh ₃ ) ₂ mmol), 80 mL of toluene, 40 mL of ethanol and 40 mL of 2 M sodium hydroxide were used to obtain 14.3 g (61.1 mmol) of Compound 175 in the same manner as in Preparation Example 1.

14.3 g (61.1 mmol) of compound 175 was dissolved in 200 mL of diethyl ether, and 57 mL (91.6 mmol) of n-butyllithium ( n- BuLi, 1.6 M in n-Hexane) was slowly added at -78 ° C, and N, N 13.7 g (91.6 mmol) of dimethylacetamide were added and then stirred at 25 ° C. for 12 hours. 50 mL of ammonium chloride was added to the reaction mixture, which was extracted with 100 mL of ethyl acetate and dried under reduced pressure to obtain 11 g (42.4 mmol) of Compound 192.

Preparation of Compound 193

Compound 154 51.4 g (146 mmol), n -butyllithium ( n- BuLi, 1.6 M in n-Hexane) 100.4 mL (160.6 mmol) chlorotriphenyl silane (Ph ₃ SiCl) (23.4 g, 219 mmol), tetrahydrofuran 44.3 g (86 mmol) of silyl intermediate compound 193 was obtained by the same method as the synthesis method of compound 155 of Preparation Example 17 using 900 mL of (THF).

Preparation of Compound 194

Tetrahydro Compound 193 in 11 g (42.4 mmol) furan (THF) into a 350 mL n - butyl lithium (n -BuLi, 1.6 M in n -Hexane) 64.5 mL (103.2 mmol), triisopropyl borate (Triisopropyl borate 33.6 g (70 mmol) of Compound 194 were obtained by the same synthesis method as Compound 156 of Preparation Example 17, using 24.3 g (129 mmol).

Preparation of Compound 195

33.6 g (70 mmol) of Compound 194 and 13.7 g (84 mmol) of 2-chloroquinoline, 200 mL of toluene and 100 mL of ethanol, 100 mL of 2M aqueous sodium carbonate solution, 1.5 g of PdCl ₂ (PPh ₃ ) ₂ 2.1 mmol) was obtained in the same manner as the compound 157 of Preparation 17, 37.2 g (66 mmol, 45% yield in 3 steps).

Compound196  Produce

37.2 g (66 mmol) of Compound 195, 9.0 g (30 mmol) of iridium chloride (IrCl 3), 600 mL of 2-ethoxyethanol and 200 mL of distilled water, using the same method as in Preparation Example 1 1196 g (41 mmol) were obtained.

Compound197  Produce

Compound 196 110.8 g (41 mmol), compound 192 phenyl (6-phenylpyridin-3-yl) methanone 31.9 g (123 mmol), AgCF ₃ SO ₃ 31.6 58.3 g (37 mmol, yield 24%) of the title compound red iridium complex pqF-23 (compound 197) was obtained in the same manner as in Preparation Example 1, using g (123 mmol) and 800 mL of 2-methoxyethyl ether. ) Was obtained.

mp. > 300 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 9 (s, 1H), 8.3 (s, 2H), 8.04-8 (m, 4H), 7.95-7.9 (m, 5H), 7.83-7.8 (m , 4H), 7.72 (d, 2H), 7.67-7.65 (m, 4H), 7.6-7.56 (m, 15H), 7.44-7.42 (m, 6H), 7.35-7.3 (m, 21H), 1.67 (s , 12H).

MS / FAB: 1609.52 (found), 1608.1 (calculated).

Preparation Example 24 Preparation of pqF-24 (Compound 200)

Preparation of Compound 198

100 g (422.1 mmol) of compound 174, 2,5-dibromo pyridine, and 90.1 g (464.3 mmol) of 4-trimethylsilyl-phenylboronic acid, PdCl 8.9 g (12.7 mmol) of ₂ (PPh ₃ ) ₂ were suspended in 300 mL of toluene, 150 mL of ethanol, and 150 mL of 2M aqueous sodium carbonate solution, followed by stirring at reflux at 130 ° C. for 12 hours. After stirring, 200 mL of distilled water was added to the reaction mixture, extracted with 200 mL of ethyl acetate, and concentrated under reduced pressure, followed by silica gel column chromatography (n-hexane: dichloromethane = 5: 1) to obtain 98.9 g (323 mmol) of Compound 198. Got.

Preparation of Compound 199

98.9 g (323 mmol) of compound 196 was added to 800 mL of diethyl ether and cooled to -78 ° C to give 389.2 mL (387.6 mmol) of n-butyllithium ( n -BuLi, 1.6 M in n-Hexane) for 30 minutes. It was added dropwise slowly, and then N, N-dimethyl-benzamide was added and (N, N -dimethyl-benzamide) 72.3 g (484.5 mmol) and stirred for 12 hours at 25 ℃. 100 mL of saturated ammonium chloride was added to the reaction mixture, followed by extraction with 300 mL of ethyl acetate and drying, followed by silica gel column chromatography (n-hex dichloromethane = 3: 1) to obtain 94.1 g (284 mmol) of Compound 199.

Preparation of Compound 200

34.8 g (20 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1, 19.9 g (60 mmol) of Compound 197, 15.4 g (60 mmol) of AgCF ₃ SO ₃ , and 250 mL of 2-methoxyethyl ether were prepared. In the same manner as in Preparation Example 1, 14.2 g (12.1 mmol, yield 10%) of the title compound, iridium complex pqF-24 (compound 200) of light red crystals, was obtained.

mp. > 300 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 9.04 (s, 1H), 8.31 (s, 2H), 8.12-8.01 (m, 4H), 7.91-7.84 (m, 7H), 7.72-7.61 (m , 10H), 7.54-7.45 (m, 9H), 7.32 (m, 2H), 1.72 (s, 12H), 0.68 (s, 9H).

MS / FAB: 1164.4 (found), 1163.5 (calculated).

Preparation Example 25 Preparation of pqF-25 (Compound 202)

Preparation of Compound 201

200 g (844.2 mmol) of 2,5-dibromopyridine, Compound 174, 113.2 g (928.6 mmol) of phenylboronic acid, and 17.8 g (25.3) of PdCl ₂ (PPh ₃ ) ₂ mmol), 600 mL of toluene, 300 mL of ethanol, and 300 mL of 2 M aqueous sodium carbonate solution to obtain 143 g (611 mmol) of Compound 175 in the same manner as in Preparation Example 1.

Then added and the resulting compound 175 143 g (611 mmol) in 1.5 L of diethyl ether was cooled to -78 ℃ n- butyllithium (n -BuLi, 1.6 M in n -Hexane) 366.6 mL (916.5 mmol) for 30 minutes while slowly added to 4-tert- butyl-N, N-dimethyl-acetamide (4-tert-butyl- N, N -dimethyl-acetamide) 150.5 g (733.2 mmol) was added and then the mixture was stirred at 25 for 12 hours ℃ The mixture was washed with 20 mL of saturated ammonium chloride, extracted with 250 mL of ethyl acetate, and dried. Then, silica gel column chromatography (n-hexane: dichloromethane = 30: 1) gave 117 g (371 mmol) of Compound 201.

Preparation of Compound 202

34.8 g (20 mmol) of the dichlorodiiridium compound of Compound 115 prepared in Preparation Example 1, 18.9 g (60 mmol) of Compound 201, 15.4 g (60 mmol) of AgCF ₃ SO ₃ , and 2-methoxyethyl ether (2- 13.9 g (12.1 mmol, 6% yield) of iridium complex pqF-25 (compound 202) of red crystals as the title compound was obtained by the same method as Preparation Example 1, using 250 mL of methoxylethylether.

mp. > 300 ℃

¹ H NMR (400 MHz, CDCl ₃ ) δ = 9.3 (s, 1H), 8.3 (s, 2H), 8.12-8.03 (m, 4H), 7.91-7.84 (m, 5H), 7.73-7.70 (m, 6H), 7,65-7.62 (m, 4H), 7.43-7.35 (m, 13H), 1.72 (s, 12H), 1.35 (s, 9H).

MS / FAB: 1145.4 (found), 1147.43 (calculated).

Preparation Example 26 Preparation of pqF-26 (Compound 208)

Preparation of Compound 205

3 g (12.7 mmol) of 9,9-dimethyl-2-acetylfluorene (compound 202) and 2-amino-6-fluorobenzophenone (compound 204) (2-amino- 2.7 g (12.7 mmol) of 6-fluorobenzophenone were suspended in 0.1 mL of concentrated sulfuric acid and 15 mL of hydrochloric acid and stirred under reflux for 24 hours. After stirring, the reaction mixture was cooled to 25 ° C., added to a mixture of 15 mL of saturated ammonium chloride and 40 mL of distilled water, and the resulting precipitate was collected, washed with water, and recrystallized with 300 mL of ethanol to obtain Compound 205 3.7 g (8.9 mmol). Got.

Preparation of Compound 206

2 g (4.8 mmol) of Compound 205, 653 mg of iridium chloride (IrCl ₃ ), (2.2 mmol), 30 mL of 2-ethoxyethanol and 10 mL of distilled water, using the same method as in Preparation Example 1 above. 1.6 g (0.8 mmol) of compound 206 was obtained.

Preparation of Compound 207

1.6 g (0.8 mmol) of Compound 206, 2.4-pentadione 152 mg (1.5 mmol), sodium carbonate 0.4 mg (3.9 mmol) and 15 mL of 2-ethoxyethanol, 1.1 g, (0.9 mmol) of compound 207 were obtained in the same manner.

Preparation of Compound 208

500 mg (0.4 mmol) of the title compound Iridium complex pqF-26 (Compound 208) in the same manner as in Preparation Example 2 using 1.1 g, (0.9 mmol) of compound 207, 1.1 g (2.7 mmol) of compound 205 and 30 mL of glycerol. , Yield 8%) was obtained.

mp. > 330 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.27 (s, 1H), 7.9 (s, 1H), 7.8 (d, 2H), 7.6 (d, 3H), 7.48 (d, 2H), 7.4 ( t, 1H), 7.32-7.3 (m, 3H), 7.22 (d, 1H), 7.1 (d, 1H), 1.73 (s, 6H).

MS / FAB: 1433.43 (found), 1435.7 (calculated).

Preparation Example 27 Preparation of pqF-27 (Compound 213)

Preparation of Compound 210

3 g (12.7 mmol) of 9,9-dimethyl-2-acetylfluorene as compound 203, 2-amino-5-fluorobenzophenone as compound 209 (2-amino- 2.7 g (12.7 mmol) of 5-fluorobenzophenone), 0.1 mL of sulfuric acid and 15 mL of hydrochloric acid were mixed and stirred under reflux for 24 hours. After the reaction was completed, the reaction mixture was cooled to 25 ° C., a mixed solution of 15 mL of ammonium chloride and 40 mL of water was poured into the cooled reaction product, the resulting precipitate was filtered under reduced pressure, washed with 200 mL of distilled water and recrystallized from 300 mL of ethanol. Compound 210 3 g (7.2 mmol) was obtained.

Preparation of Compound 211

Compound 210 2.2 g (5.3 mmol), 719 mg of iridium chloride (IrCl ₃ ), (2.4 mmol), 30 mL of 2-ethoxyethanol and 10 mL of water in the same manner as in Preparation Example 1 above 1.6 g (0.8 mmol) of compound 211 were obtained.

Preparation of Compound 212

Preparation 21.6 g (0.8 mmol), 152 mg (1.5 mmol) 2.4-pentadione (2,4-phentanedione), 0.4 mg (3.9 mmol) sodium carbonate and 15 mL 2-ethoxyethanol 1.1 g, (0.9 mmol) of compound 212 were obtained in the same manner as in 1.

Preparation of Compound 213

620 mg (0.4 mmol) of the title compound Iridium complex pqF-27 (Compound 213) in the same manner as in Preparation Example 2 using 1.1 g (0.9 mmol) of Compound 211, 1.1 g (2.7 mmol) of Compound 210 and 30 mL of glycerol. Yield 9%) was obtained.

mp. > 330 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.27 (s, 1H), 8 (d, 1H), 7.9 (s, 1H), 7.8 (d, 1H), 7.6 (d, 2H), 7.48 ( d, 2H), 7.4 (t, 2H), 7.32-7.3 (m, 4H), 7.22 (d, 1H), 1.73 (s, 6H).

MS / FAB: 1433.43 (found), 1435.7 (calculated).

Preparation Example 28 Preparation of pqF-28 (Compound 216)

Preparation of Compound 214

5 g (27.5 mmol) 2-chloro-5-fluoroquinoline, 9,9-dimethylfluorene-2-boronic acid (9,9-dimethylfluoren-2-boronic acid) 7.2 g (30.3 mmol), 150 mL of toluene, 75 mL of ethanol, 0.58 g (0.83 mmol) of PdCl ₂ (PPh ₃ ) ₂ and 75 mL of 2 M sodium carbonate were mixed and refluxed at 130 ° C. for 5 hours, then cooled to room temperature. Then, distilled water was added, extraction was performed under reduced pressure, and the compound 214 7g (20.6 mmol) was obtained.

Preparation of Compound 215

7 g (20.6 mmol) of compound 214 and 2 g (9.4 mmol) of iridium chloride (IrCl ₃ ) were added to 200 mL of a 2-ethoxyethanol: distilled water (3: 1) mixed solvent, and then It was refluxed at 130 ° C. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to yield 6 g (3.3 mmol) of Compound 215.

Preparation of Compound 216

Compound 215 6 g (3.3 mmol), 0.33 g (6.6 mmol) of 2,4-pentanedione (2,4-phenthanedione) and 1.8 g (16.5 mmol) of sodium carbonate were added thereto, followed by heating to 90 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered and extracted with 100 mL of dichloromethane. The extracted organic solution was concentrated under reduced pressure, the product was separated by silica gel column chromatography (n-hexane: dichloromethane = 10: 1), and then recrystallized with 30 mL of dichloromethane and 300 mL of n-hexane mixed solvent to obtain the title compound. 5 g (5.2 mmol, total yield 43%) of an iridium complex compound pqF-28 (compound 216) as a dark red solid was obtained.

mp. > 310 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.3 (s, 2H), 7.9 (s, 2H), 7.8 (d, 4H), 7.7 (d, 2H), 7.6 (m, 4H), 7.4 (m , 4H), 7.3 (m, 2H), 7.1 (d, 2H), 6.1 (s, 1H), 2.30 (s, 3H), 1.71 (s, 3H), 1.6 (s, 12H).

MS / FAB: 966.3 (found), 968.12 (calculated).

Preparation Example 29 Preparation of pqF-29 (Compound 219)

Preparation of Compound 217

3 g (27.5 mmol) of 2-chloro-4-fluoroquinoline and 9,9-dimethylfluorene-2-boronic acid (9,9-dimethylfluoren-2-boronic acid) 7.2 g (30.3 mmol), 150 mL of toluene, 75 mL of ethanol, 0.58 g (0.83 mmol) of PdCl ₂ (PPh ₃ ) ₂ , 75 mL of 2 M sodium carbonate were added to reflux at 130 ° C. for 5 hours, and then cooled to room temperature. Then, 200 mL of distilled water was added, extraction was performed under reduced pressure, and the compound 217 7g (20.6 mmol) was obtained.

Preparation of Compound 218

7 g (20.6 mmol) of compound 217 and 2 g (9.4 mmol) of iridium chloride (IrCl ₃ ) were added to 200 mL of 2-ethoxyethanol: distilled water (3: 1) mixed solvent, and then It was refluxed at 130 ° C. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to obtain 6 g (3.3 mmol) of Compound 218.

Preparation of Compound 219

6 g (3.3 mmol) of compound 218, 0.33 g (6.6 mmol) of 2,4-phenthanedione, and 1.8 g (16.5 mmol) of sodium carbonate were added thereto, followed by heating to 90 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered and extracted with 100 mL of dichloromethane. The extracted organic solution was concentrated under reduced pressure, the product was separated using silica gel column chromatography (n-hexane: dichloromethane = 10: 1), and then recrystallized from 30 mL of dichloromethane and 300 mL of n-hexane mixed solvent. 5 g (5.2 mmol, total yield 30%) of an iridium complex pqF-29 (compound 219) as a title compound, a dark red solid, were obtained.

mp. > 310 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.3 (s, 2H), 8.1 (d, 2H), 7.9 (s, 2H), 7.8 (d, 2H), 7.7 (d, 2H), 7.6 (m , 4H), 7.4 (m, 4H), 7.3 (m, 2H), 7.1 (s, 2H), 6.1 (s, 1H), 2.30 (s, 3H), 1.71 (s, 3H), 1.6 (s, 12H).

MS / FAB: 966.3 (found), 968.12 (calculated).

Preparation Example 30 Preparation of pqF-30 (Compound 222)

Preparation of Compound 220

3 g (10.2 mmol) of 7-tert-butyl-9,9-dimethylfluoren-2-boronic acid and 2-chloroquinoline (2- chlororquinoline) 1.5 g (9.2 mmol) was added, 50 mL of toluene, 25 mL of ethanol, 0.2 g (0.3 mmol) of PdCl ₂ (PPh ₃ ) ₂ , and 25 mL of 2 M sodium carbonate were refluxed at 130 ° C. for 5 hours. The mixture was cooled to room temperature, extracted with distilled water, and dried under reduced pressure to obtain compound 220 (2.4 g, 6.3 mmol).

Preparation of Compound 221

2.4 g (6.3 mmol) of compound 220 and 0.85 g (2.9 mmol) of iridium chloride (IrCl ₃ ) were added to 80 mL of a 2-ethoxyethanol: distilled water (3: 1) mixed solvent, and then It was refluxed at 130 ° C. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to obtain 1.4 g (0.73 mmol) of Compound 221.

Preparation of Compound 222

1.4 g (0.73 mmol) of Compound 221, 0.15 g (1.5 mmol) of 2,4-pentanedione (2,4-phenthanedione), and 0.39 g (3.7 mmol) of sodium carbonate were added thereto, followed by heating to 90 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered and extracted with 50 mL of dichloromethane. The extracted organic solution was concentrated under reduced pressure, silica gel column chromatography (n-hexane: dichloromethane = 15: 1) was carried out, and then recrystallized with 5 mL of dichloromethane and 50 mL of n-hexane mixed solvent to obtain the title compound as a dark red solid. 0.84 g (0.8 mmol, total yield 14%) of iridium complex pqF-30 (compound 222) was obtained.

mp. > 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.3 (s, 2H), 8.1 (d, 2H), 7.9 (s, 2H), 7.8 (d, 2H), 7.7 (m, 4H), 7.6 (m , 4H), 7.4 (m, 6H), 6.1 (s, 1H), 2.30 (s, 3H), 1.71 (s, 3H), 1.6 (s, 12H), 1.35 (s, 18H).

MS / FAB: 1045.42 (found), 1044.35 (calculated).

Preparation Example 31 Preparation of pqF-31 (Compound 225)

Preparation of Compound 223

5 g (16.1 mmol) of 9,9-dimethyl-7- (trimethylsilyl) fluoren-2-boronic acid and 2-chloroquinoline (2-chlororquinoline) 2.4 g ( 14.6 mmol) were dissolved, toluene 150 mL, ethanol, _{75 mL, PdCl 2 (PPh 3} ) 2 0.31 g (0.44 mmol), 2 eseo 130 ℃ for 5 hours by the addition of 75 mL M sodium carbonate After stirring under reflux, the mixture was cooled to room temperature, extracted with distilled water, and dried under reduced pressure to obtain 4.6 g (11.7 mmol) of Compound 223.

Preparation of Compound 224

4.6 g (11.7 mmol) of compound 223 and 1.6 g (5.3 mmol) of iridium chloride (IrCl 3) were added to 80 mL of a 2-ethoxyethanol: distilled water (3: 1) mixed solvent, followed by 130 for 24 hours. It was stirred at reflux at ℃. The reaction solution was cooled to room temperature, and the resulting precipitate was filtered and dried to obtain 2.7 g (1.3 mmol) of Compound 224.

Preparation of Compound 225

Compound 224 2.7 g (1.3 mmol), 2,4-pentanedione (2,4-phenthanedione) 0.27 g (2.6 mmol), sodium carbonate 0.69 g (6.5 mmol) was added and then heated to 90 ℃ for 4 hours. The reaction mixture was cooled to room temperature, and the resulting solid precipitate was filtered and extracted with 100 mL of dichloromethane. The extracted organic solution was concentrated under reduced pressure, the product was separated using silica gel column chromatography (n-hexane: dichloromethane = 15: 1), and then recrystallized from 20 mL of dichloromethane and 150 mL of n-hexane mixed solvent to obtain the title compound. 0.9 g (0.8 mmol, total yield 26%) of an iridium complex pqF-31 (compound 225) as a phosphorus dark red solid was obtained.

mp. > 270 ℃

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.3 (s, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 4H), 7.6-7.75 (m, 8H), 7.25-7.45 ( m, 8H), 6.1 (s, 1H), 2.30 (s, 3H), 1.71 (s, 3H), 0.67 (s, 12H).

MS / FAB: 1077.4 (found), 1076.5 (calculated).

Comparative Example 1 Fabrication of OLED

An OLED device was fabricated using Ir (piq) ₃ as a light emitting dopant.

First, a transparent electrode ITO thin film (15 Ω / □) obtained from an OLED glass (manufactured by Samsung Corning Corporation) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then stored in isopropanol. It was used after.

Next, the ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2-TNATA) is installed in the cell in the vacuum deposition apparatus. After the evacuation and evacuation until the vacuum in the chamber reached 10 ⁻⁶ torr, a current was applied to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate.

Then, to another cell of the vacuum vapor-deposit device N, N '-bis (α- naphthyl) - N, N' into the -diphenyl-4,4'-diamine (NPB) , and evaporation of the NPB by applying a current to the cell A 20 nm thick hole transport layer was deposited on the hole injection layer.

After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. In addition, 4,4'-N, N'-dicarbazole-biphenyl (CBP), which is a light emitting host material, is placed in another cell in the vacuum deposition apparatus, and a red light emitting compound according to the present invention is placed in another cell. A 30 nm thick light emitting layer was deposited on the hole transport layer by evaporating and doping the material at different rates. The doping concentration at this time is 4 to 10 mol% is appropriate based on CBP.

Subsequently, Bis (2-methyl-8-quinolinato) ( p- phenylphenolato) aluminum (III) (BAlq) was deposited to a thickness of 10 nm on the light emitting layer, and tris (8-hydroxyquinoline) as an electron transport layer. -Deposit aluminum (III) (Alq) to 20 nm thickness, then deposit lithium quinolate (Liq) to 1 ~ 2 nm thickness with electron injection layer, and then use other vacuum deposition equipment to make Al cathode 150 nm thick. Evaporation was carried out to produce an OLED.

Comparative Example 2 Evaluation of Optical Properties of Light-Emitting Material

An Ir (piq) ₃ complex was vacuum sublimated under 10 ^-6 torr and used as a dopant of an OLED light emitting layer to produce an OLED device. 2 shows the EL spectrum of Ir (piq) ₃ .

Example 1 Fabrication of OLED

An OLED device was manufactured using the red light emitting compound according to the present invention as a light emitting dopant.

First, a transparent electrode ITO thin film (15 Ω / □) obtained from an OLED glass (manufactured by Samsung Corning Corporation) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then stored in isopropanol. It was used after.

Next, the ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2-TNATA) is installed in the cell in the vacuum deposition apparatus. After the evacuation and evacuation until the vacuum in the chamber reached 10 ⁻⁶ torr, a current was applied to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate.

Then, to another cell of the vacuum vapor-deposit device N, N '-bis (α- naphthyl) - N, N' into the -diphenyl-4,4'-diamine (NPB) , and evaporation of the NPB by applying a current to the cell A 20 nm thick hole transport layer was deposited on the hole injection layer.

After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. In addition, 4,4'-N, N'-dicarbazole-biphenyl (CBP), which is a light emitting host material, is placed in another cell in the vacuum deposition apparatus, and a red light emitting compound according to the present invention is placed in another cell. A 30 nm thick light emitting layer was deposited on the hole transport layer by evaporating and doping the material at different rates. The doping concentration at this time is 4 to 10 mol% is appropriate based on CBP.

Subsequently, Bis (2-methyl-8-quinolinato) ( p- phenylphenolato) aluminum (III) (BAlq) was deposited to a thickness of 10 nm on the light emitting layer, and tris (8-hydroxyquinoline) as an electron transport layer. -Deposit aluminum (III) (Alq) to 20 nm thickness, then deposit lithium quinolate (Liq) to 1 ~ 2 nm thickness with electron injection layer, and then use other vacuum deposition equipment to make Al cathode 150 nm thick. Evaporation was carried out to produce an OLED.

Example 2 Evaluation of Optical Properties of Light-Emitting Material

Complexes with high synthetic yields for each material were vacuum sublimed and purified under 10 ^-6 torr to be used as dopants for OLED emitting layers. However, only the PL properties of pqF-21 and pqF-28 were low due to low synthesis yields.

In order to confirm the performance of the OLED manufactured in Example 1, the luminous efficiency was measured at 1000 cd / m ² , and various characteristics are shown in Tables 1 and 2 below.

TABLE 1

Table 1 shows the device characteristics of the luminescent material synthesized by introducing a hydrogen substituent to the substitution position from R ₁ to R ₁₀ by introducing a main ligand and various auxiliary ligands. Table 1 shows excellent color coordinates with the maximum EL wavelength of 618 nm and color coordinates (0.67,0.32) of the tris-chelated complex structure of n = 3, and it shows that the luminous efficiency was higher than the color coordinates with 8.0 cd / A. Can be. When n = 2 and L '= acac, the ultra-large EL wavelength shifted by 2 nm toward longer wavelengths than when n = 3, which is expected to shift to longer wavelengths because of less steric hindrance of ligands bound to the iridium metal center. do. The luminescent materials synthesized using the auxiliary ligand acac derivative show wavelength ranges of about 618 ~ 620 nm, and do not affect the color coordinates very much. Also, the luminous efficiency shows 7.5 cd / A. It can be seen that it exhibits good light emission characteristics.

The luminescent materials synthesized using hetero ligands as auxiliary ligands exhibit various emission wavelength ranges from 604 to 622 nm, so they not only have various emission ranges from orange to pure red, but also pqF, a luminescent material using ppy as an auxiliary ligand. In the case of -8, it can be seen that a high luminous efficiency of 9.5 cd / A.

Accordingly, according to the present invention, the main ligand can be tuned to a desired emission wavelength by immobilizing the main ligand using the properties of various auxiliary ligands.

[Table 2]

Table 2 shows the device properties of the light emitting material consisting of a main ligand and an auxiliary ligand having a hydrogen or alkyl substituent in the substitution position of R ₁ to R ₁₀ . It can be seen from Table 2 that the light emitting material has various emission wavelength ranges according to the auxiliary ligands, which are shown in Table 1 above.

Various alkyl substituents were introduced into the fluorene moiety of the main ligand, and the emission wavelength band was determined according to the electron-donating or electron-withdrawing characteristics of the substituent. At this time, the wavelength range is readjusted by the auxiliary ligand, so that the emission wavelength can be tuned more precisely.

In particular, pqF-17, a light emitting material using trimethyl silyl (TMS) group and Rphenyl ₉ as an auxiliary ligand, using phenylpridine (PPY), exhibits a light emission efficiency of 618 nm and high 9.7 cd / A.

1 is a cross-sectional view of an OLED, and FIGS. 2 to 5 show EL spectra, current density-voltage characteristics, luminance-driving voltage characteristics, and light emission of OLEDs employed as pqF-2 and pqF-17 dopants, which are red phosphorescent compounds according to the present invention. The efficiency-luminance characteristics are shown.

The emission wavelength of the OLED device using pqF-2 and pqF-17 can be confirmed from FIG. 2, and both dopants exhibit excellent color coordinate characteristics because the emission wavelength is narrower than that of 2-phenyl isoquinoline [Ir (piq) ₃ ].

3 to 5 show current density-voltage characteristics, luminance-driving voltage characteristics, and luminous efficiency-luminance characteristics of OLED devices using pqF-2 and pqF-17, and pqF-2 and pqF at luminance 1000 cd / m ² . -17 all show high efficiency above 8 cd / A.

Since the red light emitting compound according to the present invention is a compound having a better skeleton than the conventional red phosphorescent material and exhibits excellent EL properties than the existing material, if the red light emitting compound according to the present invention is applied to an OLED panel, You can expect more advanced results.

Claims (6)

An organic light emitting compound represented by Formula 1 below. [Formula 1]

L is an organic ligand; R ₁ to R ₁₀ are each independently hydrogen, halogen, straight-chain or branched-chain alkyl group of the alkyl group, C _{1 -20} alkoxy group, C _{6 -20} aryl, C _{1 -20} of the substituted C _{1 -20} C _{6 -20} aryl group, a heterocyclic or heteroaryl of C _{5 -20} aryl group, a ketone group, an alkyl silyl C _{1 -20,} arylsilyl, alkylaryl silyl, dicyano ethylene group or, with an adjacent substituent C _{2 -} connected to alkylene of C _{2 -10} that contain a ₁₀ alkylene or a fused ring to form an alkyl ring, or a fused ring, an alkyl which is formed by the alkyl groups of the C _{2 -20,} an alkoxy group, an aryl group and an alkylene The ring or fused ring may be substituted with one or more halogen or phenyl groups; R ₁₁ and R ₁₂ are independently a C _{1 -12} straight or branched chain alkyl group, C _5-10 cycloalkyl group, C _{6 -10} aromatic ring, C _{1 -20} alkyl group is substituted with a C _{6 -20} of one another aromatic ring, or C _{6 -20} of the hetero ring or heteroaromatic ring; n is 1 to 3. The method of claim 1, Ligand L is an organic light emitting compound having the structure:

R ₂₁ and R ₂₂ are each independently hydrogen, a halogen substituted or unsubstituted C _{1 -7} straight-chain or branched-chain alkyl group, a C _{1 -7} straight-chain or branched-chain alkyl group is an optionally substituted phenyl group or a halogen ego; R ₂₃ to R ₂₆ independently represent hydrogen, linear or branched alkyl group of C _{1 -7,} C _{1 - 7} alkyl silyl group, or a halogen; R ₂₇ is a phenyl group or a halogen are straight or branched chain alkyl group or straight or branched chain alkyl group of C _{1 -7} of a C _{1 -7} which is optionally substituted. The method of claim 2, Ligand L is an organic light emitting compound having the structure:

The method of claim 1, R ₁ to R ₁₀ are each independently hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, fluoro, trimethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t -Butyldimethylsilyl, triphenylsilyl, phenyldimethylsilyl or phenyl, R ₁₀ and R ₁₁ are independently of each other methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-octyl, 2 An organic light emitting compound that is ethylhexyl. The method of claim 4, wherein An organic light emitting compound selected from the following compounds.

An organic light emitting device comprising the organic light emitting compound according to claim 1.

Images