KR20150009274A - Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device - Google Patents

Abstract

The present invention relates to a novel iridium (III) complex, a manufacturing method thereof, and an organic electronic device using the same. More specifically, provided are a novel iridium (III) complex which has excellent thermal stability by a compound forming a ring and excellent light emitting efficiency through introduction of core or ligand in which electron density is excellent; a manufacturing method thereof; and an organic electronic device including the novel iridium (III) complex.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting material for an organic electroluminescent device, an organic electroluminescent device using the same, and a material for an organic electroluminescent device,

The present invention relates to a novel iridium (III) complex, a method for producing the same, and an organic electronic device using the same. More specifically, the present invention relates to a novel iridium (III) complex having excellent applicability, luminescent efficiency and thermal stability And an organic electronic device including the derivative.

In general, organic light emitting diodes (OLEDs) are composed of a cathode (eg, aluminum or lithium aluminum), a cathode (eg, ITO), and an organic layer interposed between the cathode and anode. (EL), an electron transport layer (ETL), an electron transport layer (EIL), a hole injection layer (HIL), a hole transport layer (HTL) LiAl or the like, and one or two organic layers may be omitted if necessary. When an electric field is applied between the electrodes, electrons are injected into the cathode and holes are injected into the anode. Further, the electrons recombine with the holes in the light emitting layer to generate an excited state, and emit energy as light when the excited state returns to the ground state.

Such a light emitting material is largely divided into fluorescence and phosphorescence. The method of forming a light emitting layer includes a method of doping a fluorescent host (pure organic material) with phosphorescence (organic metal), a method of doping a fluorescent dopant (organic material including nitrogen etc.) And a method of implementing a long wavelength using a dopant (DCM, Rubrene, DCJTB, etc.) on a light emitting body. Such doping is intended to improve the emission wavelength, efficiency, driving voltage, lifetime, and the like.

In general, HIL has 2-TNATA (4,4 ', 4 "-tris- (N- (naphthylen-2-yl) , 4 '' - Tris (N-3-methylphenyl-N-phenylamino) triphenylamine), TCTA (4,4 ', 4-tris (triphenylamine) ) And the like are used, and HTL is a-NPD (4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), OA-3 (N1, N1- ) -N4- (4- (dibiphenyl-4-ylamino) phenyl) -N4-phenylbenzene-1,4-diamine), Spiro-TPD (N2, N2, N2 ', N2', N7, N7, N7 ' (PEDOT: PSS [poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)] is used for the solution process. ] Is used.

The ETL can also be selected from the group consisting of Alq3 (Tris (8-hydroxyquinolinato) aluminum), L01 (9,10-di (quinolin-2-yl) anthracene), TmPyPB (1,3,5- ) benzene) is used as a common layer of OLED. ETL materials for solution process are currently under development, and so far, this part has been conducting performance tests of emissive materials through deposition.

The material for forming the light emitting layer may be selected from the group consisting of benzene, naphthalene, fluorene, spiroprolene, anthracene, pyrene and carbazole and a ligand such as phenyl, biphenyl, naphthalene and heterocycle and ortho, Cyanide, fluorine, methyl, trimethyl, and the like.

For example, in the case of blue, there is a compound such as a, b-ADN, b, b-MADN and BD1 in the above compound and green is represented by Indeno [1,2,3- cd] perylene, 5,12-diphenyltetracene and ATCDA Structures can be used, and red is Sony's BSN, Kodak's DCM2, and Idemitsu's PI.

The phosphorescent compounds are the above-mentioned compounds, and the orange light emitting compounds are the typical compounds of Ir (pq) ₂ acac containing quinoline. The luminescence efficiency of Ir (pq) ₂ acac was 14 cd / A at 7 V (Bull. Korean Chem. Soc. 2010, Vol.31, No. 10 2955).

In the future, display OLEDs and OLEDs for illumination will require phosphorescent compounds for solution process rather than physical vapor deposition (PVD), which can be mass produced at low cost. This is because phosphorescent compounds show higher performance in low molecular weight than fluorescent compounds.

The present invention seeks to provide an organic electrical device comprising the novel iridium (III) complex capable of such a solution process.

The present invention provides a novel iridium (III) complex exhibiting excellent luminescence efficiency through introduction of a core or a ligand excellent in thermal stability and excellent electron density by a compound that forms a ring, do.

The present invention also provides an organic electroluminescent device including the novel iridium (III) complex.

The present inventors provide a novel iridium (III) complex represented by the following general formulas (1) to (3) for improving the performance of the aromatic compound and the device that form the ring.

[Chemical Formula 1]

IrL ¹ L ² L ³

In the above formula (1), the ligands L ¹ to L ³ independently of one another are represented by the following formula (2) or (3), and at least one of the ligands should be represented by the formula (2) or (3).

(2)

(3)

(2) or (3)

X is on each occurrence, the same or differently, N (nitrogen), O (oxygen), S (sulfur), and, X is N (nitrogen) in the case m ₁ to m ₅ is an integer of 1, O (oxygen) Or S (sulfur), m ₁ to m ₅ are integers of 0. n ₁ and n ₂ are integers of 0 or 1, and m ₆ + m ₇ ≥ 1.

Ar ₁ and Ar ₉ are a 5- or 6-membered heterocycle containing N (nitrogen), Ar ₂ to Ar ₈ may be the same or different from each other, and the number of the substituted or unsubstituted carbon atoms is 7 - Substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkylthiol groups having 7 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms , A substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylthiol group having 6 to 50 carbon atoms, an unsubstituted or carbon An amine group substituted with an aryl group having 6 to 50 atoms, a silyl group, and a phosphine oxide group.

Y ₁ to Y ₅ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 Substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyl thiol groups having 7 to 50 carbon atoms, A substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted carbon atom An arylthiol group having a number of 6 to 50, an amine group substituted with an unsubstituted or aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.

,

,

,

등으로, R은 5 또는 6원의 헤테로환을 함유한 화합물)들은 제외한다.In the formula (2) or (3), when n ₁ and n ₂ are integers of 0, Ar ₁ and Ar ₃ having a material name of n, n + 1 (1,2-, 2,3-, 9,10-, ₄ and Ar ₆ (

,

,

,

, R is a compound containing 5 or 6-membered heterocycle) are excluded.

In another aspect of the present invention, there is provided an organic electronic device comprising the novel iridium (III) complex of Formula 1.

The novel iridium (III) complexes according to the present invention can form various cores of Ar ₁ to Ar ₆ in the general formulas (1) to (3) and improve the emission wavelength and performance by improving electron density. In addition, it is possible to control the fine emission wavelength and improve the performance by controlling the ligand molecular weight of Y ₁ to Y ₅ and the kind of the ligand.

In addition, the organic electronic device using the novel iridium (III) complex according to the present invention has high luminance, excellent heat resistance, long lifetime and high efficiency.

Hereinafter, the present invention will be described in detail. The following detailed description is only illustrative of the present invention, and thus the present invention is not limited thereto.

According to one aspect of the present invention, there is provided a novel iridium (III) complex represented by the following general formula (1).

[Chemical Formula 1]

IrL ¹ L ² L ³

In the above formula (1), the ligands L ¹ to L ³ independently of one another are represented by the following formula (2) or (3), and at least one of the ligands should be represented by the formula (2) or (3).

(2)

(3)

(2) or (3)

X is on each occurrence, the same or differently, N (nitrogen), O (oxygen), S (sulfur), and, X is N (nitrogen) in the case m ₁ to m ₅ is an integer of 1, O (oxygen) Or S (sulfur), m ₁ to m ₅ are integers of 0. n ₁ and n ₂ are integers of 0 or 1, and m ₆ + m ₇ ≥ 1.

Ar ₁ and Ar ₉ are a 5- or 6-membered heterocycle containing N (nitrogen), Ar ₂ to Ar ₈ may be the same or different from each other, and the number of the substituted or unsubstituted carbon atoms is 7 - Substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkylthiol groups having 7 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms , A substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylthiol group having 6 to 50 carbon atoms, an unsubstituted or carbon An amine group substituted with an aryl group having 6 to 50 atoms, a silyl group, and a phosphine oxide group.

Y ₁ to Y ₅ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 Substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyl thiol groups having 7 to 50 carbon atoms, A substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted carbon atom An arylthiol group having a number of 6 to 50, an amine group substituted with an unsubstituted or aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.

,

,

,

등으로, R은 5 또는 6원의 헤테로환을 함유한 화합물)들은 제외한다.In the formula (2) or (3), when n ₁ and n ₂ are integers of 0, Ar ₁ and Ar ₃ having a material name of n, n + 1 (1,2-, 2,3-, 9,10-, ₄ and Ar ₆ (

,

,

,

, R is a compound containing 5 or 6-membered heterocycle) are excluded.

The definition of terms used in this specification will be described in detail as follows.

, 시아노기, 치환 또는 비치환된 아미노기(-NH₂, -NH(R), -N(R')(R''), R'과 R"은 서로 독립적으로 탄소수 1 내지 10의 알킬기임), 아미디노기, 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알케닐기, C1-C20의 알키닐기, C1-C20의 헤테로알킬기, C6-C20의 아릴기, C6-C20의 아릴알킬기, C6-C20의 헤테로아릴기, 또는 C6-C20의 헤테로아릴알킬기로 치환될 수 있다. 이러한 알킬기의 예로서 메틸, 에틸, 프로필, 2-프로필, n-부틸, 이소-부틸, tert-부틸, 펜틸, 헥실, 도데실, 플루오로메틸, 디플루오로메틸, 트리플루오로메틸, 클로로메틸, 디클로로메틸, 트리클로로메틸, 요오도메틸, 브로모메틸 등을 들 수 있다. "Alkyl group" means a straight or branched saturated monovalent hydrocarbon portion of a carbon atom. The at least one hydrogen atom contained in the alkyl group may be substituted with a halogen atom, a silyl group, a phosphine oxide group, a hydroxyl group, -SH, a nitro group,

, A cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms) A C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C1-C20 alkenyl group, a C1-C20 alkynyl group, a C1-C20 alkynyl group, An aryl group of C6-C20, an arylalkyl group of C6-C20, a heteroaryl group of C6-C20, or a heteroarylalkyl group of C6-C20. Examples of such alkyl groups include methyl, ethyl, Propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, , Bromomethyl and the like.

The "aryl group" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety, and at least one hydrogen atom of the aryl group may be substituted with the same substituent as the alkyl group. The aromatic moiety of the aryl group contains only carbon atoms. Examples of aryl groups include phenyl, naphthalenyl and fluorenyl.

 Means a monovalent monocyclic or bicyclic aromatic radical having 1, 2 or 3 heteroatoms selected from N, O or S and the remaining ring atoms C, The term also refers to monovalent monocyclic or bicyclic aromatic radicals in which the heteroatoms in the ring are oxidized or tanned to form, for example, N-oxides or quaternary salts. Representative examples include thienyl, benzothienyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, quinoxalinyl, imidazolyl, furanyl, benzofuranyl, thiazolyl, isoxazoline, Benzimidazolyl, benzimidazolyl, benzimidazolyl, triazolyl, pyrazolyl, pyrrolyl, indolyl, 2-pyridonyl, N-alkyl-2-pyridonyl, pyridazinonyl, pyridazinonyl, , Oxazolonyl, and the corresponding N-oxides (e.g., pyridyl N-oxide, quinolinyl N-oxide), quaternary salts thereof, and the like. At least one hydrogen atom in the heterocyclic group may be substituted with the same substituent as the alkyl group.

"Amine group substituted with an aryl group" One or more hydrogen atoms of the amino group are substituted with an aryl group, and at least one hydrogen atom of the aryl group can be substituted with the same substituent as the aryl group.

"Aralkyl" or "arylalkyl" means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and at least one hydrogen atom of the aralkyl group may be substituted with the same substituent as the alkyl group. Examples thereof include benzyl, benzhydryl and trityl.

The terms "alkoxy group "," aralkyloxy group ", and "aryloxy group" refer to a form in which oxygen is further contained at the linkage bonding sites of the aforementioned "alkyl group", "aralkyl group" Alkylthio group "and" arylthio group "refer to a form in which sulfur is further contained at the linkage bonding sites of the" aralkyl group "and the" aryl group ".

 "Bond" refers to a moiety attached only to a simple bond without any substituent attached thereto.

Wherein Y ₁ to Y ₅ are as described above, at least one hydrogen attached to these carbons, and may be substituted with independently different substituents to each other, and examples thereof include an amino group, a cyano group, a silyl group, a hydroxyl group, or There may be, but is not limited to, a phosphine oxide group.

The above Chemical Formulas 1 to 3 may be represented by Chemical Formula 4 or Chemical Formula 5:

[Chemical Formula 4]

[Chemical Formula 5]

In the formula (4) or (5)

X is in each case the same or different from N (nitrogen), O (oxygen), S (sulfur) and m is from ₈ to ₁₀ when X is N (nitrogen) Or S (sulfur), m ₈ to m ₁₀ are integers of 0. n ₃ and n ₄ are integers of 0 or 1, and m ₁₁ + m ₁₂ ≥ 1.

Ar ₁₀ and Ar ₂₀ are a 5- or 6-membered heterocycle containing N (nitrogen), Ar ₁₁ to Ar ₁₉ may be the same or different from each other, and the number of the substituted or unsubstituted carbon atoms is 7 - Substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkylthiol groups having 7 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms , A substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylthiol group having 6 to 50 carbon atoms, an unsubstituted or carbon A silyl group, or a phosphine oxide group, and Ar ₁₁ to Ar ₁₇ may be fused to form a substituted or unsubstituted ring when two adjacent substituents are fused to each other. have. Y ₆ to Y ₈ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 Substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyl thiol groups having 7 to 50 carbon atoms, A substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted carbon atom An arylthiol group having a number of 6 to 50, an amine group substituted with an unsubstituted or aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.

More specific embodiments of the above Chemical Formulas 1 to 3 can be represented by the following compounds:

According to another aspect of the present invention there is provided a process for the preparation of a compound of formula (I) as defined in any one of claims 1 to 3, comprising the step of carrying out an amination reaction and a debenzoylation and a Suzuki coupling reaction. A process for preparing a novel aromatic amine compound.

(I) Synthesis of S-1 and S-2 using benzoyl in the case of benzoyl, ZH of S-1 and S-2 is -OH, -SH and benzoyl, II) synthesizing S-3 through an amination reaction of s-1 and S-2, (III) removing S-4 from benzoyl when S-3 contains benzoyl, (IV) synthesizing S-5 by performing amination reaction of Y ₁ to Y ₃ when S-4 is -NH-, (V) synthesizing S- (III) complexes comprising the steps of: (a) reacting a compound of formula (I) with a compound of formula

X, Ar ₁ to Ar ₃ , Y ₁ to Y ₃ , m ₁ and m ₂ of the S-5 and n ₁ are as defined above in the formula (2).

Preferred embodiments are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easy understanding of the present invention, and the present invention is not limited thereto.

In addition, it is understood that the compound in which the preparation method is not specifically disclosed in each of the examples of the present invention, may be prepared by a method customary in the art or by referring to the preparation method described in other examples.

≪ Preparation of intermediate &

Intermediate (1-1). Preparation of 4-bromo-1- (3-bromophenyl) -1H-pyrazole

9 g (68 mmol) of 4-bromo-1H-pyrazole, 19.8 g (70 mmol) of 1-bromo-3-iodobenzene, 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in a xylene solvent Thereafter, the reaction was carried out at 180 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and 200 ml of toluene was added thereto. The mixture was filtered through a suction filter, passed through a silica gel column, concentrated and washed with an ethyl acetate / methanol mixed solvent to obtain 15.2 g of solid compound 1-1 74%.

Intermediates (1-2, 1-3).

As a method for producing the above intermediate (1-1), the following compounds of Table 1 were obtained:

Intermediate Starting material Product material yield(%) 1-2

68% 1-3

70%

Intermediate (1-4). Preparation of 4-bromo-2- (3-bromo-5-fluorophenyl) pyridine

(50 mmol) of 4-bromopyridin-2-ylboronic acid, 15.9 g (53 mmol) of 1-bromo-3-fluoro-5-iodobenzene, 50 ml of a 2 M aqueous solution of sodium carbonate and 100 ml of 1,2-dimethoxyethane , 0.59 g (0.5 mmol) of tetrakis (triphenylphosphine) palladium was added to the mixed solution, and the mixture was refluxed for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with toluene using a separatory funnel. The organic layer was dried over anhydrous magnesium sulfate, concentrated by a filter, and purified by silica gel chromatography (eluent: hexane: toluene = 8: 2). This was recrystallized with hexane to obtain 79% of a solid compound 1-4 (16.5 g).

* Intermediate (2-1). Preparation of N, N-bis (3-bromophenyl) benzamide

(34 mmol) benzamide, 16.5 g (70 mmol) of 1,3-dibromobenzene, 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in a xylene solvent, For 3 hours. After lowering the temperature, 10.9 g (35 mmol) of 1,3-dibromobenzene was dissolved in 100 ml of a xylene solvent, and the mixture was reacted at 180 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 300 ml of toluene was added, and the mixture was filtered through a suction filter, passed through a silica gel column, concentrated and washed with an ethyl acetate / methanol mixed solvent to obtain solid compound 2-1 (10.7 g) %.

Intermediate (2-2). Preparation of N, N '- (3,3'-oxybis (3,1-phenylene)) dibenzamide

(34 mmol) benzamide, 5.9 g (18 mmol) of 3,3'-oxybis (bromobenzene), 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in a xylene solvent, Lt; 0 > C for 3 hours. After lowering the temperature, 10.9 g (35 mmol) of 1,3-dibromobenzene was dissolved in 100 ml of a xylene solvent, and the mixture was reacted at 180 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 300 ml of toluene was added, and the mixture was filtered through a suction filter, passed through a silica gel column, concentrated and then washed with an ethyl acetate / methanol mixed solvent to obtain 78% of solid compound 2-2 did.

* Preparation of intermediate (2-3, 2-12).

As a method for producing the above intermediate (2-2), the following compounds in Table 2 were obtained:

Intermediate Starting material Product material yield(%) 2-3

68% 2-4

73% 2-5

75% 2-6

69% 2-7

72% 2-8

74% 2-9

69% 2-10

71% 2-11

65% 2-12

73%

* Preparation of intermediate (3-1).

(35 mmol) of 4-bromo-2- (3-bromophenyl) pyridine, 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were added to a xylene solvent After dissolving, the mixture was reacted at 180 ° C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 300 ml of toluene was added thereto, and the mixture was filtered through a suction column to remove inorganic salts and the like, passed through a silica gel column, concentrated and washed with an ethyl acetate / methanol mixed solvent to obtain solid compound 3-1 %.

Preparation of intermediates (3-2, 3-8).

As a method for producing the above intermediate (3-1), the following compounds of Table 3 were obtained:

Intermediate Starting material Product material yield(%) 3-2

68% 3-3

72% 3-4

67% 3-5

75% 3-6

72% 3-7

65% 3-8

67%

* Preparation of intermediate (3-9).

N-bis (3-bromophenyl) benzamide (2-1), 3.6 g (35 mmol) benzene-1,3-diamine, 7.8 g (81.6 mmol) sodium tert- , 300 ml of o-xylene was added, and the mixture was refluxed for 2 hours. After the temperature was lowered to room temperature, 0.9 ml of tri-tert-butylphosphine solution (0.012 g) and bisacetylpalladium (II) were added thereto, followed by refluxing for another 20 hours. After completion of the reaction, the solvent was evaporated in vacuo, and THF (200 m) was added thereto, followed by filtration and concentration. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 58 g of 3-9 (7.4 g).

Preparation of intermediate (3-10).

N, N '- (3,3'-oxybis (3,1-phenylene)) dibenzamide (2-2), 8.0 g (34 mmol) 1,3-dibromobenzene, 7.8 g (81.6 mmol) of sodium-tert-butoxide and 300 ml of o-xylene was added thereto, followed by refluxing for 2 hours. After the temperature was lowered to room temperature, 0.9 ml of tri-tert-butylphosphine solution, 0.012 g of bisacetyl palladium (II) was added, and the mixture was further refluxed for 20 hours. When the reaction was completed, the solvent was vacuum-dried, and THF (200 m) was added, followed by filtration, followed by concentration and purification by silica gel chromatography (toluene / hexane = 1/6) to obtain 3-10 (10.2 g) 62%.

Preparation of intermediates (3-11, 3-60).

As a method for producing the above intermediate (3-10), the following compounds of Table 4 were obtained:

Intermediate Starting material Product material yield(%) 3-10 2-3

64% 3-11 2-4

65% 3-12 2-4

60% 3-13 2-4

58% 3-14 2-4

55% 3-15 2-4

57% 3-16 2-4

61% 3-17 2-4

60% 3-18 2-5

63% 3-19 2-6

59% 3-20 2-7

61% 3-22 2-8

54% 3-33 2-9

50% 3-34 2-10

56% 3-35 2-11

49% 3-36 2-12

55% 3-37 2-5

57% 3-38 2-6

55% 3-39 2-7

61% 3-40 2-8

57% 3-41 2-9

51% 3-42 2-10

53% 4-43 2-11

48% 3-44 2-12

52% 3-45 2-5

55% 3-46 2-6

61% 3-47 2-7

65% 3-48 2-8

55% 3-49 2-9

48% 3-50 2-10

53% 3-51 2-11

51% 3-52 2-12

55% 3-53 2-5

57% 3-54 2-6

61% 3-55 2-7

59% 3-56 2-8

62% 3-57 2-9

48% 3-58 2-10

53% 3-59 2-11

50% 3-60 2-12

54%

* Preparation of intermediate (4-1).

7.4 g (18 mmol) of Intermediate 3-7 was dissolved in a xylene solvent, 1.7 g (30 mmol) of potassium hydroxide and 40 ml of 2-propanol were added, and the mixture was reacted at 70 ° C for 1 hour. After 2-propanol was removed, 50 ml of toluene was added and the mixture was refluxed for 1 hour. After filtration at 50 DEG C, the filtrate was dried to obtain 95% of solid compound 4-1 (5.3 g).

* Preparation of intermediates (4-2, 4-44).

As a method for producing the above intermediate (4-1), the compound shown in the following [Table 5] was obtained:

Intermediate Product material yield(%) Intermediate Product material yield(%) 4-2

92% 4-3

94% 4-4

90% 4-5

89% 4-6

93% 4-7

90% 4-8

87% 4-9

95% 4-10

91% 4-11

93% 4-12

94% 4-13

95% 4-14

93% 4-15

91% 4-16

90% 4-17

88% 4-18

89% 4-19

88% 4-20

91% 4-21

94% 4-22

90% 4-23

93% 4-24

89% 4-25

89% 4-26

88% 4-27

88% 4-28

91% 4-29

95% 4-30

93% 4-31

94% 4-32

88% 4-33

86% 4-34

89% 4-35

89% 4-36

91% 4-37

93% 4-38

92% 4-39

94% 4-40

94% 4-41

89% 4-42

91% 4-43

87% 4-44

93%

* Preparation of intermediate (6-1).

(36 mmol) of 2- (4-bromophenyl) pyridine, 0.6 g (10 mmol) of copper, 5 g (36 mmol) of dried potassium carbonate and 0.5 g of sodium persulfate in 10.5 g Then, 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 占 폚, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 57% of 6-1 (8.9 g).

* Preparation of intermediate (6-2).

As a method for producing Intermediate 6-1, 59% of 6-2 (8.6 g) was obtained.

* Preparation of intermediate (6-3).

52% of Intermediate 5-1 (7.5 g) was obtained using Intermediate 4-3 and 11 g (70 mmol) of [Addition (1)] as an amination preparation method for Intermediate 6-1, yield Intermediate 5 (4.3 g) was obtained in a yield of 54% by use of 8.4 g (36 mmol) of 2- (4-bromophenyl) pyridine [added (2)].

Preparation of intermediate (6-4, 6-6).

As a method of producing the above intermediate (6-3), the following compounds of Table 6 were obtained:

Intermediate Starting material Additives (1) Additives (2) Product material yield(%) 6-4 4-4 1-bromo-4-fluorobenzene 2- (4-bromophenyl) pyridine

31% 6-5 4-5 bromobenzene 2- (4-bromophenyl) pyridine

29% 6-6 4-6 bromobenzene 1- (4-bromophenyl) -1H-pyrazole

27%

Preparation of intermediate (6-7).

Using Intermediate 4-7 and 11 g (70 mmol) of bromobenzene, 62% of Intermediate 6-7 (10.3 g) was obtained in the same manner as Intermediate 6-1.

Preparation of intermediate (6-8, 6-44).

As a method for producing the above intermediate (6-7), the following compounds of Table 7 were obtained:

Intermediate Starting material Product material yield(%) 6-8 4-8 bromobenzene

58% 6-9 4-9 bromobenzene

55% 6-10 4-10 Bromobenzene

52% 6-11 4-11 Bromobenzene

55% 6-12 4-12 Bromobenzene

59% 6-13 4-13 bromobenzene

63% 6-14 4-14 bromobenzene

60% 6-15 4-15 bromobenzene

57% 6-16 4-16 bromobenzene

53% 6-17 4-17 bromobenzene

49% 6-18 4-18 bromobenzene

56% 6-19 4-19 bromobenzene

48% 6-20 4-20 bromobenzene

51% 6-21 4-21 bromobenzene

58% 6-22 4-22 bromobenzene

53% 6-23 4-23 bromobenzene

57% 6-24 4-24 bromobenzene

55% 6-25 4-25 bromobenzene

48% 6-26 4-26 bromobenzene

53% 6-27 4-27 bromobenzene

50% 6-28 4-28 bromobenzene

56% 6-29 4-29 bromobenzene

61% 6-30 4-30 bromobenzene

59% 6-31 4-31 bromobenzene

60% 6-32 4-32 bromobenzene

57% 6-33 4-33 bromobenzene

46% 6-34 4-34 bromobenzene

52% 6-35 4-35 bromobenzene

49% 6-36 4-36 bromobenzene

53% 6-37 4-37 bromobenzene

57% 6-38 4-38 bromobenzene

55% 6-39 4-39 bromobenzene

58% 6-40 4-40 bromobenzene

56% 6-41 4-41 bromobenzene

51% 6-42 4-42 bromobenzene

50% 6-43 4-43 bromobenzene

47% 6-44 4-44 bromobenzene

52%

Example 1. Preparation of 8-1

Under nitrogen, 18.4 g (40 mmol) of 6-1, 3.6 g (10 mmol) of IrCl ₃ -3H ₂ O, 100 ml of 2-ethoxyethanol and 35 ml of water were added to the flask and refluxed for 16 hours. After cooling to room temperature and precipitation, the precipitate was filtered and washed with ethanol and hexane to give 89% of the iridium compound 7-1 (20.4 g). 20.4 g (9 mmol) of the obtained iridium compound 7-1 was dissolved in dichloromethane, and 2.4 g (9 mmol) of silver (Ag) triflate was dissolved in isopropanol and then added to the iridium compound solution. The solution was stirred at room temperature for 20 hours, then filtered to remove the silver chloride and vacuum dried. 12.4 g (27 mmol) of 6-1 was added thereto, and an ethanol solvent was added thereto, followed by refluxing for 16 hours. The solution was purified by column chromatography (dichloromethane) and vacuum dried. The obtained product was washed with 2-propanol and hexane and dried to obtain 8-1 (5.7 g) of 40%.

* Preparation of Examples 2 to 21 (8-2, 8-26).

The compound of the following [Table 8] was obtained by the production method of Example 1 (8-1)

Example Starting material Product material yield(%) Example 2
(8-2) 6-2

38% Example 3
(8-3) 6-3

41% Example 4
(8-4) 6-4

39% Example 5
(8-5) 6-5

34% Example 6
(8-6) 6-6

36% Example 7
(8-7) 6-7

39% Example 8
(8-8) 6-8

40% Example 9
(8-9) 6-9

42% Example 10
(8-10) 6-10

36% Example 11
(8-11) 6-13

35% Example 12
(8-12) 6-14

37% Example 13
(8-13) 6-15

35% Example 14
(8-14) 6-16

41% Example 15
(8-15) 6-17

35 Example 16
(8-16) 6-18

37% Example 17
(8-17) 6-19

33% Example 18
(8-18) 6-20

35% Example 19
(8-19) 6-21

39% Example 20
(8-20) 6-22

40% Example 21
(8-21) 6-23

41% Example 22
(8-22) 6-24

34% Example 23
(8-23) 6-25 32% Example 24
(8-24) 6-26

39% Example 25
(8-25) 6-27

35% Example 26
(8-26) 6-28

40%

* Preparation of Example 27 (8-27).

13.5 g (40 mmol) of Intermediate 3-1, 3.6 g (10 mmol) of IrCl ₃ -3H ₂ O, 100 ml of 2-ethoxyethanol and 35 ml of water were placed in a flask under a nitrogen atmosphere and refluxed for 16 hours. After cooling to room temperature to precipitate, the precipitate was filtered and washed with ethanol and hexane to give 90% of the iridium compound 7-27 (11.3 g). 11.3 g (9 mmol) of the obtained iridium compound 7-27, 2.3 g (23 mmol) of 2,4-pentanedione and 0.1 g of sodium carbonate were dissolved in 2-ethoxyethanol and refluxed for 15 hours. After cooling to room temperature, the precipitate was filtered and washed with water. Chromatography (dichloromethane) separated and dried to give 8-27 (4.2 g) 75%.

* Preparation of Examples 28 to 25 (8-28, 8-30).

The compound of the following [Table 9] was obtained by the preparation method of Example 27 (8-27)

Example Starting material Product material yield(%) Example 28
(8-28) 3-2

72% Example 29
(8-29) 3-3

68% Example 30
(8-30) 3-4

81%

* Preparation of Example 31 (8-31).

A-1, 7.5 g (23 mmol) of intermediate 3-5 and 0.1 g of sodium carbonate were added to a solution of 6.9 g (9 mmol) of the iridium compound obtained in the same manner as in the synthesis of 7-27 in the same manner as in the synthesis of Example 27, -Ethoxyethanol and refluxed for 15 hours. After cooling to room temperature, the precipitate was filtered and washed with water. Chromatography (dichloromethane) and separation and drying gave 8-31 (4.0 g) 66%.

* Preparation of Examples 32-50 (8-32, 8-60).

The compound of the following [Table 10] was obtained by the production method of Example 31 (8-31)

Example Starting material Product material yield(%) Example 32
(8-32) 3-6

68% Example 33
(8-33) 6-11

63% Example 34
(8-34) 6-12

61% Example 35
(8-35) 6-29

67% Example 36
(8-36) 6-30

64% Example 37
(8-37) 6-31

63% Example 38
(8-38) 6-32

66% Example 39
(8-39) 6-33

58% Example 40
(8-40) 6-34

63% Example 41
(8-41) 6-35

58% Example 42
(8-42) 6-36

60% Example 43
(8-43) 6-37

65% Example 44
(8-44) 6-38

61% Example 45
(8-45) 6-39

62% Example 46
(8-46) 6-40

59% Example 47
(8-47) 6-41

60% Example 48
(8-48) 6-42

65% Example 49
(8-49) 6-43

59% Example 50
(8-50) 6-44

63%

<Experimental Example>

The glass substrate coated with the ITO thin film with a thickness of 1500 Å was put into the second distilled water in which the detergent of the fisher was melted and was ultrasonically cleaned for 30 minutes. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent of isopropyl alcohol, acetone, and methanol, dried, transferred to a plasma cleaner, and the substrate was cleaned for 5 minutes using oxygen plasma.

A PEDOT / PSS (hole injecting material) aqueous solution was spin-coated on the substrate to form a hole injection layer having a thickness of 40 nm. Next, PVK dissolved in monochlorobenzene and the comparative material (Ir (pq) ₂ acac) containing 8% or the materials of Example 11 were formed by spin-coating a 50 nm thick light emitting layer on the dried hole injection layer . Subsequently, Alq ₃ was vacuum-deposited on the dried light emitting layer to a thickness of 30 nm, and then an anode was vacuum-deposited to a thickness of 1 nm of LiF and 100 nm of Al to prepare an OLED.

The electroluminescent characteristics of the organic light-emitting device prepared above are shown in Table 11 below.

The light- Current density
(mA / cm ² ) color efficiency
(cd / A) life span
(hrs) Comparative substance Ir (pq) ₂ AcAc 20 Orange 2.8 1,700 Experimental Example Example 2 20 Orange 5.2 3,200 Example 3 20 Red 4.3 2,800 Example 5 20 Red 4.7 2,500 Example 7 20 Orange 7.9 5,300 Example 27 20 green 11.5 9,300 Example 28 20 green 9.3 7,600 Example 32 20 green 10.2 8,700 Example 34 20 Orange 6.2 4,800 Example 44 20 Orange 5.7 4,500 Example 48 20 Orange 5.5 4,300

From the results of the above Table 11, it can be confirmed that the novel iridium (III) complex according to the present invention can emit various colors, and the luminous efficiency and lifetime characteristics are improved in the role of a dopant of orange color.

The organic luminescent device using the novel iridium (III) complex of the present invention has improved luminous efficiency and lifetime. Based on these results, the novel iridium (III) complexes of the present invention are industrially useful because they are highly practical.

INDUSTRIAL APPLICABILITY The organic light emitting device of the present invention can be suitably used for a light source such as a flat panel display, a planar light emitting body, a light emitting body of a surface emitting OLED for illumination, a flexible light emitting body, a copying machine, a printer, an LCD backlight or a meter, a display plate,

Claims (7)

A novel iridium (III) complex represented by the following formula
[Chemical Formula 1]
IrL ¹ L ² L ³
In the above formula (1), the ligands L ¹ to L ³ independently of one another are represented by the following formula (2) or (3), and at least one of the ligands should be represented by the formula (2) or (3).
(2)

(3)

(2) or (3)
X is on each occurrence, the same or differently, N (nitrogen), O (oxygen), S (sulfur), and, X is N (nitrogen) in the case m ₁ to m ₅ is an integer of 1, O (oxygen) Or S (sulfur), m ₁ to m ₅ are integers of 0. n ₁ and n ₂ are integers of 0 or 1, and m ₆ + m ₇ ≥ 1.
Ar ₁ and Ar ₉ are a 5- or 6-membered heterocycle containing N (nitrogen), Ar ₂ to Ar ₈ may be the same or different from each other, and the number of the substituted or unsubstituted carbon atoms is 7 - Substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkylthiol groups having 7 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms , A substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylthiol group having 6 to 50 carbon atoms, an unsubstituted or carbon An amine group substituted with an aryl group having 6 to 50 atoms, a silyl group, and a phosphine oxide group.
Y ₁ to Y ₅ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 Substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyl thiol groups having 7 to 50 carbon atoms, A substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted carbon atom An arylthiol group having a number of 6 to 50, an amine group substituted with an unsubstituted or aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.
In the formula (2) or (3), when n ₁ and n ₂ are integers of 0, Ar ₁ and Ar ₃ having a material name of n, n + 1 (1,2-, 2,3-, 9,10-, ₄ and Ar ₆ (

,

,

,

, R is a compound containing 5 or 6-membered heterocycle) are excluded.
The method according to claim 1,
The novel iridium (III) complex represented by the general formula (2) or (3) is represented by the following general formula (4) or (5)
[Chemical Formula 4]

[Chemical Formula 5]

In the formula (4) or (5)
X is in each case the same or different from N (nitrogen), O (oxygen), S (sulfur) and m is from ₈ to ₁₀ when X is N (nitrogen) Or S (sulfur), m ₈ to m ₁₀ are integers of 0. n ₃ and n ₄ are integers of 0 or 1, and m ₁₁ + m ₁₂ ≥ 1.
Ar ₁₀ and Ar ₂₀ are a 5- or 6-membered heterocycle containing N (nitrogen), Ar ₁₁ to Ar ₁₉ may be the same or different from each other, and the number of the substituted or unsubstituted carbon atoms is 7 - Substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkylthiol groups having 7 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms , A substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylthiol group having 6 to 50 carbon atoms, an unsubstituted or carbon A silyl group, or a phosphine oxide group, and Ar ₁₁ to Ar ₁₇ may be fused to form a substituted or unsubstituted ring when two adjacent substituents are fused to each other. have. Y ₆ to Y ₈ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 Substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyl thiol groups having 7 to 50 carbon atoms, A substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted carbon atom An arylthiol group having a number of 6 to 50, an amine group substituted with an unsubstituted or aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.
The method according to claim 1,
A novel iridium (III) complex, characterized in that it is selected from compounds of the following structure:

An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the electrodes,
Wherein at least one layer of the organic material layer comprises the novel iridium (III) complex according to any one of claims 1 to 3. 5. The method of claim 4,
The organic material layer may include a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer, And at least one of the functional layers. 5. The method of claim 4,
Wherein the organic electronic device is an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoconductor (OPC), or an organic transistor (OTFT). A process for producing a novel aromatic amine compound according to any one of claims 1 to 3, comprising a step of carrying out an amination reaction and a debenzoylation reaction and a suzuki coupling reaction.

(I) Synthesis of S-1 and S-2 using benzoyl in the case of benzoyl and ZH of S-1 and S-2 are -OH, -SH and benzoyl II) synthesizing S-3 through an amination reaction of s-1 and S-2, (III) removing S-4 from benzoyl when S-3 contains benzoyl, (IV) synthesizing S-5 by performing amination reaction of Y ₁ to Y ₃ when S-4 is -NH-, (V) synthesizing S- (III) complexes comprising the steps of: (a) reacting a compound of formula (I) with a compound of formula
X, Ar ₁ to Ar ₃ , Y ₁ to Y ₃ , m ₁ and m ₂ of the S-5 and n ₁ are as defined above in the formula (2).