WO2004111066A1

WO2004111066A1 - Metal coordination compound, polymer composition, and organic electroluminescence element using them

Info

Publication number: WO2004111066A1
Application number: PCT/JP2004/008392
Authority: WO
Inventors: Satoyuki Nomura; Yoshii Morishita; Yoshihiro Tsuda
Original assignee: Hitachi Chemical Co., Ltd.
Priority date: 2003-06-09
Filing date: 2004-06-09
Publication date: 2004-12-23
Also published as: KR20060027323A; TW200504175A

Abstract

A metal coordination compound, characterized in that it is represented by one of the following formulae (1) to (6): (1) to (6) [wherein, B represents >NR, >O, >S, >C=O, >SO2, or >CR2; M represents Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3; when M is Ir, Rh, Ru or Os and n is 2, M is further bonded with another bi-dentate ligand; and the ring A is a cyclic group containing a nitrogen atom bonded to M]. And also provided is a phosphorescence emitting material which emits a light in a wide visible region from blue to red and also is excellent in the purity of color, reliability and the like.

Description

Metal coordination compound, polymer composition, and organic electroluminescent device using the same

Technical field

Light

The present invention relates to a novel metal coordination compound, a polymer composition, and a fine composition using the same.

The present invention relates to an organic electroluminescence (EL) device.

Background art

In recent years, electroluminescent devices have attracted attention for large area solid-state light source applications as alternatives to incandescent lamps and gas-filled lamps. On the other hand, it is attracting attention as the leading self-luminous display that can replace the liquid crystal display in the flat panel display (FPD) field. In particular, organic electroluminescent (EL) devices, which are made of organic materials, are being commercialized as low-power-consumption full-color FPDs.

Until now, general organic EL devices have extracted fluorescence when the excited singlet relaxes to the ground state. However, the ratio of excitons formed by injecting charge into an organic thin film is statistically said to be singlet: triplet = 1: 3, and the theoretical limit value of the internal quantum efficiency of an organic EL device is 25 %It is said that. This has been an obstacle to reducing the power consumption of organic EL devices.

As one means to solve this problem, an element using phosphorescence from the excited triplet has been studied. If phosphorescence from the excited triplet can be used, at least three times the emission quantum yield can be obtained, in principle, than if fluorescence from the excited singlet is used. Can be expected. Furthermore, considering the use of excitons by intersystem crossing from singlet to triplet from the singlet with high energy, a luminescence quantum yield of 4 times, that is, 100% can be expected in principle.

Examples of research to date include, for example, M.A. Baldo et al., Appl. Phys. Lett. 1999.75. In this document, the following materials are used. Abbreviations of each material are as follows.

A 1 q 3: Aluminum quinolinol complex (tris (8-quinolinolato) aluminum) α— NPD: N, -Di-naphthalen-l-yl-N, N'-diphenyl-biphenyl-4, 4'- diamine

CBP: 4, 4'-N, N'-dicarbazole-biphenyl

B C P: 2, 9-dimethyl-4, 7-diphenyl-l, 10-phenanthrol ine

I r (ppy) ₃ : iridium-phenylpyridine complex (tris (2-phenylpyridine) iridium)

Other examples using light emission from an excited triplet include JP-A-11-313297, JP-A-11-256148, and JP-A-8-319482. Disclosure of the invention

However, it is difficult to provide an organic EL device which emits light at various wavelengths from blue to red and has excellent reliability with the above-mentioned materials utilizing light emission from the excited triplet. Accordingly, an object of the present invention is to provide a phosphorescent material which emits light in a wide visible light range from blue to red and has excellent color purity, reliability, and the like in view of the above-described conventional problems. .

In particular, when the above-mentioned full-color organic EL device using phosphorescence was to be produced, a metal coordination compound having blue phosphorescence having good color purity was found. Not. Accordingly, an object of the present invention is to provide a metal coordination compound having blue phosphorescence with excellent color purity.

In particular, when considering not only the above-mentioned full-color organic EL device using phosphorescence but also lighting applications, the phosphorescent metal distribution having various luminescent colors and a long driving life is provided. Development of coordination compounds is desired. However, the driving life of phosphorescent devices has been shorter than that of fluorescent devices. It is not clear why the driving lifetime of the phosphorescent device is short, but generally the lifetime of the excited triplet state is longer than that of the excited singlet, and the molecule stays in the high energy state for a long time. It is thought that reactions, structural changes in the molecules themselves, and reactions between excitons may occur. Therefore, an object of the present invention is to provide a metal coordination compound which emits light of various colors from green to red and has a long driving life. In particular, when attempting to produce an organic EL device for full-color or lighting applications using phosphorescence, no metal coordination compound having blue phosphorescence with good color purity has been found. In addition, no blue to red material with a long drive life has been found. Accordingly, an object of the present invention is to provide a metal coordination compound having blue phosphorescence having excellent color purity, and to provide a metal coordination compound having phosphorescence having a long driving life from blue to red. It shall be.

Another object of the present invention is to provide a polymer composition containing the metal coordination compound.

Still another object of the present invention is to provide an organic electroluminescent device using the metal coordination compound or the polymer composition. As a result of intensive studies, the inventors of the present invention have found that a metal coordination compound having a cyclic compound represented by formulas (1) to (6) as a ligand emits light in a wide wavelength range from blue to red. Completed the present invention by finding that it is a phosphorescent material with excellent properties I came to. That is, the present invention relates to a compound represented by any of formulas (1) and (6).

(one two Three)

B:>NR,>0,>S,> C = 0,> S〇 ₂ ,> CR

(Where M is Ir, Rh, Ru, 〇s, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or Os and n is 2 , M is further bound to another bidentate ligand Ring A is a cyclic compound containing a nitrogen atom bonded to M. XJ XB and R are each independently R —〇R ² , SR ³ , —〇C〇R ⁴ , _C〇〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , and one NR ⁹ R ¹⁰ (however, a length of ¹ to! ^ ¹³ is a hydrogen atom, a halogen atom, a cyano group , Nitro group, carbon number 1-2 Two straight-chain, cyclic or branched alkyl groups or a halogen-substituted alkyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms, an aryl group having 6 to 21 carbon atoms, a carbon number of 2 to 2 A heteroaryl group of 20 or an aralkyl group having 7 to 21 carbon atoms or a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which part or all of the hydrogen atoms have been replaced by halogen atoms. Express,! ^ ¹ ~! ^ ¹ . May be the same or different. ) Comprising a substituent selected from the group of, also, X I through X ₆ is independently selected from groups a same ring A the same groups defined X _t to X ₆ It may have a substituent. Here, 1 ^ to ^{11 (} may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, and a carboxyl group. And a sulfonic acid group, a nitro group, etc. These substituents may be further substituted with a halogen atom, a methyl group, or the like.

In addition, the inventors of the present invention have found that a metal coordination compound having a carbazole derivative as a ligand is an excellent phosphorescent material having blue phosphorescence with excellent color purity. I found it. Therefore, as a preferred embodiment of the present invention, there is provided a metal coordination compound represented by any one of the following formulas I (1) to 1 (6).

I- (1) I- (2) I- (3)

I-(4) I- (5) I-(6)

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or Os and n is 2, Another bidentate ligand is bound to M. Ring A is a cyclic compound containing a nitrogen atom bound to M. Xi X? Is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a charcoal A straight-chain, cyclic or branched alkyl group having 1 to 22 prime atoms, or a halogen-substituted alkyl group in which part or all of hydrogen atoms have been substituted with halogen atoms, an aryl group having 6 to 21 carbon atoms, and 2 carbon atoms Any of a halogen-substituted aryl group, a halogen-substituted heteroaryl group, a halogen-substituted heteroaryl group, and a halogen-substituted aralkyl group in which some or all of the hydrogen atoms thereof are substituted with a halogen atom. may be in, also, ~; ₇ It may be the same or different and ring A may have the same substituent groups as defined in Xi~X _7. )

In addition, the inventors of the present invention have found that, in particular, a metal coordination compound in which various substituents have been introduced into a ligand as a ligand has a luminescent color ranging from green to red, and has a long drive life. It has been found that it is a long and excellent phosphorescent material.

Therefore, as a preferred embodiment of the present invention, there is provided a metal coordination compound represented by any of the following formulas II (1) to (6).

Π- (1) II- (2) 11- (3)

Wherein M is Ir, h, Ru, 〇s, Pd or Pt, and n is 2 or 3. M is Ir, Rh, Ru or 〇s and n is 2 In this case, M is further bound to another bidentate ligand Ring A is a cyclization containing a nitrogen atom bonded to M It is a compound. Xi～X ₇ is independently - H, -〇_H, -R ^1, -OR ^2, one

SR ³ , one OCOR ⁴ , —COOR ⁵ , — S i R ⁶ R ⁷ R ⁸ , — NH ₂ , one NHR 9

, And one NR ^ R ¹¹ (where ¹ to! ^ ¹ is a straight-chain, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, and 2 to 20 carbon atoms) Represents an aralkyl group having 7 to 21 carbon atoms, and each of R ¹ to shaku ¹¹ may be the same or different.) A substituent selected from the group consisting of , Or eh ~? It may be the same or different and ring A may have the same substituent groups as defined in Xi~X _7. Here, Ri R ¹¹ may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a lipoxyl group, Examples thereof include a sulfonic acid group and a nitrile group. These substituents may be further substituted by a halogen atom, a methyl group, or the like.

In addition, the inventors of the present invention have proposed that a metal coordination compound having a cyclic compound represented by formulas III (1) to ΙΙΙ (6) as a ligand can emit phosphorescent light from blue to red having excellent color purity. It has been found that this is an excellent phosphorescent material having a long driving life.

Accordingly, as a preferred embodiment of the present invention, there is provided a metal coordination compound represented by any of the following formulas III (1) to (6).

III- (l) 111- (2) 111- (3)

111- (4) III- (5) ΙΠ-(6)

B:>O,> S, > C = 0,> S0 2,> CR,

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or Os and n is 2, Another bidentate ligand is bonded to M. Ring A is a cyclic compound containing a nitrogen atom bonded to M. X _{1 to} X ₆ and R are each independently — R ¹ -OR ² , — SR ³ , _〇COR ⁴ , one C〇〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , and one NR ⁹ R ¹⁰ (where ¹ to! ^^ are a hydrogen atom, a halogen atom, a cyano group A nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms or a halogen-substituted alkyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms, a carbon atom having 6 to 21 carbon atoms Aralkyl group having 2 to 20 carbon atoms or aralkyl group having 7 to 21 carbon atoms, or a halogen-substituted aryl group in which part or all of the hydrogen atoms have been replaced with halogen atoms, a halogen-substituted heteroaryl group And a halogen-substituted aralkyl group, and 1 ^ to ^{11 ()} may be the same or different. ) A substituent selected from the group consisting of, also, Xi Xe may be different even in the same ring A have the same substituent groups as defined in Xi～X ₆ It may be. ) In this case, scale ¹ ~! ^ ^1. May have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a lipoxyl group, a sulfonic acid group, and a nitro group. Can be mentioned. These substituents may be further substituted by a halogen atom, a methyl group or the like. '

The present invention also relates to a polymer composition obtained by mixing or copolymerizing the metal coordination compound with a conjugated or non-conjugated polymer.

The present invention also relates to an organic electroluminescent device manufactured using the metal coordination compound or the polymer composition.

The disclosure of the present application is related to the subjects described in Japanese Patent Application Nos. 2003-164321, 2003-164328, and 2003-164340 filed on June 9, 2003, and the disclosure contents thereof are cited. Hereby incorporated by reference. BEST MODE FOR CARRYING OUT THE INVENTION

The metal coordination compound of the present invention is represented by the following formulas (1) to (6).

(one two Three)

B:>NR,>〇,>S,> C = 0,> S〇 ₂ ,> CR

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or 〇s and n is 2 , M further binds another bidentate ligand Ring A is a cyclic compound containing a nitrogen atom bonded to M. Xi Xe and R each independently represent one R ¹ , — OR ² , _SR ³ , —〇COR ⁴ , one C〇OR ⁵ , one Si R ⁶ R ⁷ R ⁸ , and one NR ⁹ R ¹⁰ (where 1 ^ to 1 ^ ^{1 ()} is a hydrogen atom, a halogen atom, a cyano group A nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen-substituted alkyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms, a carbon atom having 6 to 21 carbon atoms. Aralkyl groups having 2 to 20 carbon atoms or aralkyl groups having 7 to 21 carbon atoms, or halogen-substituted araryl groups in which some or all of the hydrogen atoms thereof have been replaced by halogen atoms; heteroaryl group halogen substituted, a halogen-substituted Ararukiru group, scale ¹ ~! ^ ^{1 15} may each be the same or different. X i X e may be the same or different, and ring A is the same substituent as the group defined by X i to X ₆ It may have a group. Here, 1 ^ to ^{11 (} may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, Examples include a ropoxyl group, a sulfonic group, a nitro group, etc. These substituents may be further substituted by a halogen atom, a methyl group, or the like.

Examples of the substituents represented by XiXe and R are shown below, but the present invention is not limited thereto.

Examples of —R ¹ include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a cyano group, a nitro group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, and a butyl group. Group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group , Phenyl, tolyl, xylyl, mesityl, cumenyl, benzyl, phenethyl, methylbenzyl, diphenylmethyl, styryl, cinnamyl, biphenyl, terphenyl, naphthyl, anthryl , Fluorenyl group, furan residue, thiophene residue Group, pyrrole residue, oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, quinoxaline residue or a fluorine atom or chlorine atom Atom, bromine And halogen-substituted compounds substituted with an iodine atom or the like.

- Examples of OR ² represents a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, tert- butoxy group, Okuchiruokishi group, tert- Okuchiru Okishi group, phenoxy group, 4-tert- Buchirufuenokishi group, 1 one-naphthyl Okishi Group, 2-naphthyloxy group and 9-anthryloxy group.

Examples of SR ³ include mercapto group, methylthio group, ethylthio group, tert-butylthio group, hexylthio group, octylthio group, phenylthio group, 2-methylphenylthio group, and 4_tert-butylphenylthio group. be able to.

Examples of OCOR ⁴ include a formyloxy group, an acetoxy group, and a benzoyloxy group.

Examples of COOR ⁵ include a carbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a phenoxycarbonyl group, and a naphthyloxycarbonyl group.

One Examples of ^{^{^{S i R 6 R 7 R 8}}} , can be mentioned silyl group, a trimethylsilyl group, Toryechi Rushiriru group, a triphenyl silyl group.

Examples of NR ⁹ R ^{1 ()} include amino, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-ethylamino, N, N-diisopropylamino, N , N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N, N-diphenylamino group and the like.

The metal coordination compound of the present invention has phosphorescent emission, and the lowest excited state is considered to be a triplet MLCT (Metal-to-Ligand charge transfer) excited state or a π-excited state. . When transitioning from these states to the ground state Phosphorescence occurs.

The phosphorescent quantum yield of the light emitting material of the present invention was as high as 0.1 to 0.9, and the phosphorescence lifetime was 1 to 60 s. The short phosphorescence lifetime is a condition for increasing the luminous efficiency of an organic EL device. In other words, if the phosphorescence lifetime is long, the proportion of molecules in the excited triplet state increases, and at high current densities, the luminous efficiency is reduced based on the 1 τ annihilation. The metal coordination compound of the present invention is a material suitable for a luminescent material of an organic EL device because it has a high phosphorescent efficiency and a short luminescent life.

Among the metal coordination compounds represented by the formulas (1) to (6), the ring ことが is preferably any one of the cyclic compounds having a structure shown below, and more preferably X i X e (hereinafter, X i X e , May be collectively referred to as a substituent X n.), Which may have the same substituent as the group defined in —pyridine, quinoline, benzoxazole, benzothiazol, benzimidazole, benzotriazole, It is imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole, triazine or isoquinoline.

()

9ΐ

Z6C800 / l700Zdf / X3d 990 contract OAV Here, Zi Ze is the same substituent as the substituent represented as Xn in formulas (1) to (6), and Zi Ze may be the same or different.

In the present invention, in the formulas (1) to (6), M is preferably Ir.

When the metal M is Ir, Rh, Ru, 〇s, and n = 2, the other ligand that binds to the metal M may be any of the compounds having the structures shown below. preferable.

Equation (8)

here

Are the same substituents as the substituent represented as Xn of the formula (1) ~ (6), Yi~Y 4 may be different even in the same.

(Detailed description of synthesis method of metal coordination compound)

Hereinafter, the method for synthesizing the metal coordination compound of the present invention will be described in detail using specific examples of the metal coordination compound.

The metal coordination compound of the present invention can be produced by various synthetic methods known to those skilled in the art. For example, the method described in S. Lamansky et al., J. Am. Chem. Soc. 2001.123. Can be used. An example (in the case where ring A is substituted pyridine) of a synthesis route of the metal coordination compound represented by the above formulas (1) to (6) used in the present invention will be described by taking an iridium coordination compound as an example. Note that the explanations here relate to (2) shown in Table I-11, (2) shown in Table II-1, and (2) shown in Table III-1. The exemplified compounds can be synthesized by almost the same method. (Synthesis of ligand L)

Ligand L in Table 1-1 (2) or Table II (1)

Table III—Ligands L in 1 (2)

(Synthesis of iridium complex)

3XL

lr (CH ₃ COCHCOCH ₃ ) ₃ → ^ lr (L) ₃

Grycerin, microwave: 30min or

Acetylacetonate 2CO3

IrCI ₃ XH ₂ 0 or Na ₃ lrCI ₆ 2H ₂ 0- [lr (L) ₂ Ci] ₂ lr (L) ₂ (CH ₃ COCHCOCH ₃ )

2-Ethoxyethanol-water _t rt: 30min reflux: 24h 2-Ethox ethanol- _t reflux: 15h lr (L) ₂ (GH ₃ COCHCOCH ₃ ) lr (L) ₃

Glycerol, 180C: 8

Preferred embodiments of the metal coordination compound of the present invention are shown below.

(Metal coordination compounds represented by formulas I (1) to 1 (6))

In order to obtain blue phosphorescence in organic EL, the lowest excited state A high level of energy is required. However, it is considered that the emission level of the metal coordination compound has changed from blue-green to red because the energy level of the lowest excited state was low for blue light emission.

Therefore, the present inventors have conducted various studies and found that the metal coordination compounds represented by the following formulas I (1) to 1 (6) have blue phosphorescence.

I-(1) I-(2) I-(3)

1- (4) I-(5) 1- (6)

(Where Μ is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or 〇s and n is 2 , M further binds another bidentate ligand Ring A is a cyclic compound containing a nitrogen atom bonded to M. ェ ~? Are hydrogen atom, halogen atom, cyano group, nitro group, A straight-chain, cyclic or branched alkyl group having 1 to 22 carbon atoms or a hydrogen atom thereof Halogen-substituted alkyl groups partially or wholly substituted with halogen atoms, aryl groups having 6 to 21 carbon atoms, heteroaryl groups having 2 to 20 carbon atoms, or aralkyls having 7 to 21 carbon atoms A halogen-substituted aryl group, a halogen-substituted heteroaryl group, or a halogen-substituted aralkyl group, in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom; To X ₇ may be the same or different, and ring A may have the same substituent as the group defined for X i to X ₇ . )

Among the formula I (1) ~ metal coordination compound represented by 1 (6), ring A is preferably either a cyclic compound having the structure shown below, X I through X ₇ (hereinafter, Pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole which may have the same substituent as the group defined in). Oxazole, thiazole, triazole, benzopyrazole or triazine, more preferably pyridine or quinoline which may have the same substituent as the group defined by Xn.

(I)

Z6 £ 800 contract Zdf / IOd 990 contract ΟΛ \ Here Zi～Z ₆ are the same substituents as the substituent represented as Xn of formula I (1) ~ I (6 ), Z Ze may or may not be the same.

Equation I (8)

Here Y to Y ₄ are the same substituents represented as Xn of formula I (1) ~1 (6) , Yi~Y 4 may be different even in the same.

In the metal coordination compounds represented by the above formulas I (1) to 1 (6), at least one of the substituents Xn, or at least one of the substituents defined in the same manner as Xn included in ring A, has a shorter emission wavelength. From the viewpoint of being effective for the above, it is preferably a halogen atom, a cyano group or a halogen-substituted alkyl group, more preferably a fluorine atom, a chlorine atom, a cyano group or a trifluoromethyl group, and It is more preferably an orthomethyl group, and most preferably a fluorine atom. When at least one of the substituents Xn or the substituents defined in the same manner as the Xn of the ring A has any of the above substituents, the other Xn is often a hydrogen atom, May be a substituent of For example, X ₇ is preferably an alkyl group or a halogen-substituted alkyl group. Among the metal coordination compounds represented by the formulas I (1) to 1 (6), synthesis is easy. From the viewpoint, it is preferable that the metal coordination compound is represented by the formula I (1) or I (4).

The metal coordination compounds represented by the formulas I (1) to 1 (6) are expected to have a high energy level in the lowest excited state, and are suitable as a blue phosphorescent material for organic EL.

Specific examples of the metal coordination compounds represented by the above formulas I (1) to 1 (6) are shown below, but are not limited thereto. In addition, X to X ₄ in Table 1-1 represent a substituent of ring A.

Table I—1

(Synthetic specific examples of metal coordination compounds represented by formulas I (1) to I (6))

23/1

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26 26/1

26 26/2

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27/2

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30

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Z6C800 / 1-00Zdf / X3d 990ΪΪ 囊 OZ ΟΛ \ 31

(Metal coordination compounds represented by formulas 11 (1) to II (6))

To obtain phosphorescence from green to red in organic EL, it is necessary to change the energy level of the lowest excitation state. In addition, the lifetime of the excited triplet state is generally longer than that of the excited singlet, and the molecule stays in the high-energy state for a long time. Therefore, it is thought that the driving life of the phosphorescent device was short with the conventional metal coordination compounds.

Therefore, the present inventors have conducted various studies and found that the metal coordination compounds represented by the following formulas II (1) to 11 (6) have phosphorescence emission from green to red and have a long driving life. It has been found to be a phosphorescent material.

II- (l) I (2) 11- (3)

11- (4) II-(5) II- (6) 32

Wherein M is Ir, Rh, Ru, 〇s, Pd or Pt, and n is 2 or 3. M is Ir, Rh, Ru or 〇s and n is 2 In this case, another bidentate ligand is bonded to M. Ring A is a cyclic compound containing a nitrogen atom bonded to M. Xi to X ₇ are each independently —H, -OH, — R ¹ -OR ² , one SR ³ , one OC〇R ⁴ , one CO〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , one NH ₂ , one NHR ⁹ , and one NR ^ R ¹¹ (where ¹ ~! ^ ¹¹ is a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or 7 to Represents an aralkyl group of 21 and R ¹ to ¹¹ may be the same or different.) And Xi X is the same or different Ring A is the same as the group defined by Xi X? May have the following substituents.) Here,! ^ To shaku ¹¹ may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a lipoxyl group, and a sulfonic acid group. And nitro groups. These substituents may be further substituted by a halogen atom, a 'methyl group or the like.

Among the metal coordination compounds represented by the formulas II (1) to 11 (6), ring A is preferably any one of the cyclic compounds having the structures shown below, and Xe to _r (hereinafter, referred to as Xe to _r ). Pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imitriazolyl, pyridine, quinoline, benzoxazole, benzothiazole, which may have the same substituent as the group defined in). , Pyrazole, oxazole, thiazole, triazole, benzopyrazole, triazine or isoquinoline, and pyridine, quinoline or isoquinoline which may have the same substituent as the group defined by Xn Is more preferred.

34

Here, Zi Ze is the same substituent as the substituent represented by Xn in formulas II (1) to (6), and Z _{1 to} Z ₆ may be the same or different.

Equation II (8)

Here Yi～Y ₄ are the same substituents as the substituent represented as Xn of the formula II (1) ~11 (6) , Y 1 ~Y 4 may or may not be the same.

In the metal coordination compounds represented by the above formulas II (1) to 11 (6), at least one of the substituents X η or at least one of the substituents defined similarly to Xn of the ring まで is green to red. From the viewpoint of easy control of the emission color of, it is preferable to be 1 R, 1 OR or 1 SR. When at least one of the substituents Xn or the substituents defined in the same manner as Xn in the ring A has any of the above substituents, the other Xn is often a hydrogen atom, It may be another substituent. For example, X ₇ is preferably an alkyl group, an aryl group or a heteroaryl group.

Among the metal coordination compounds represented by the formulas II (1) to 11 (6), the metal coordination compound represented by the formula II (1) or II (4) from the viewpoint of easy synthesis Force S preferred.

The metal coordination compounds represented by the above formulas II (1) to 11 (6) have various substituents. 35

As a result, the energy level of the lowest excited state changes, making it suitable as an organic EL light emitting material that emits green to red light.

Specific examples of the metal coordination compounds represented by the formulas II (1) to (6) are shown below, but are not limited thereto. Note that Table II Xi~X ₄ in one 1 represents a substituent of the ring Alpha.

Table II-1

: Specific examples of the synthesis of metal coordination compounds represented by formulas II (1) to (6)

36/1

Paper (Rule 2β) 37

(Rule 26) 37/1

Paper (Rule 2β) 38

(Rule 2β) 38/1

(Rule 2β) 39

(Rule 26) 39/1

(Rule 2β)

41

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(Rule 26) 42

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Paper (Rule 2β) 43/1

Paper (Rule 2β)

Z6C800 / l700Zdf / X3d 990 contract OAV

45

Paper (Rule 2β) 45/1

(Metal coordination compounds represented by formulas III (1) to III (6))

To obtain phosphorescence from blue to red in organic EL, it is necessary to change the energy level of the lowest excitation state. In addition, the lifetime of the excited triplet state is generally longer than that of the excited singlet, and the molecule stays in the high-energy state for a long time. It is thought that the driving life of the phosphorescent light-emitting element was short because of the occurrence of this phenomenon. .

Thus, the present inventors have conducted various studies, and found that the metal coordination compounds represented by the following formulas III (1) to III (6) emit phosphorescence from blue to red and have a long driving life. It has been found that it becomes a light emitting material.

Replacement paper (¾ J) 46

III- (l) 111- (2) ΙΠ- (3)

111- (4) III-(5) ΙΠ- (6)

B:> O,〉 S,> C = O,〉 SO ₂ ,> CR

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or 〇s and n is 2 , M is further bound to another bidentate ligand Ring A is a cyclic compound containing a nitrogen atom bonded to M. X Xe and R are each independently — R ¹ , -OR ² , One SR ³ , one C〇R ⁴ , one C〇〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , and one NR ⁹ R ¹⁰ (however,! ^ ¹ ~! ^ ¹ is a hydrogen atom, halogen Atom, cyano group, nitro group, straight-chain, cyclic or branched alkyl group having 1 to 22 carbon atoms or a halogen-substituted alkyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms, carbon number 6-21 47

Aralkyl group having 2 to 20 carbon atoms or aralkyl group having 7 to 21 carbon atoms, or a halogen-substituted aryl group in which part or all of the hydrogen atoms thereof have been replaced with halogen atoms, a halogen-substituted heteroaryl group group, a halogen-substituted Ararukiru radical, R E ~ ^{1 Q} may each be the same or different. Xi Xe may be the same or different, and ring A has the same substituent as the group defined by Xi Xe May be. ) Where ¹ ~! ^ ¹ . May have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a lipoxyl group, a sulfonic acid group, and a nitro group. Can be mentioned. These substituents may be further substituted by a halogen atom, a methyl group or the like. .

Among the formula III (1) a metal coordination compound represented by to III (6), ring A is preferably either a cyclic compound having the structure shown below, X i to X ₆ (hereinafter, The pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazol, imidazole, and pyrazole which may have the same substituent as the group defined in) are collectively denoted as Xn. , Oxazole, thiazole, triazole, benzopyrazole, triazine or isoquinoline, and pyridine, quinoline or isoquinoline which may have a substituent similar to the group defined by Xn Is more preferred. 48

― _N

r., N

49

Here, Zi Ze is the same substituent as the substituent represented as X η in Formulas III (1) to ΙΠ (6), and Zi to Z _δ may be the same or different.

When the metal is Ir, Rh, Ru, or Os, and n = 2, the other ligand bonded to the metal M is preferably any of the compounds having the structures shown below.

Formula III (8)

Here Υ ~Υ ₄ are the same substituents as the substituent represented as Xn of the formula III (1) ~III (6) , Yi~Y 4 may be different even in the same.

In the metal coordination compounds represented by the above formulas III (1) to (6),

Χη or at least one of the substituents defined in the same manner as Xn of the ring ことが is preferably an octogen atom, a cyano group or a halogen-substituted alkyl group from the viewpoint of obtaining a blue emission color. It is more preferably a fluorine atom, a chlorine atom, a cyano group or a trifluoromethyl group, further preferably a fluorine atom or a trifluoromethyl group, and most preferably a fluorine atom. In addition, from the viewpoint of easy control of the emission color from blue to red, —R, —OR, or —SR is preferable. When at least one of the substituents Xn or the substituents defined in the same manner as Xn of the ring A has any of the above substituents, the other Xn is often a hydrogen atom, It may be a substituent.

Among the metal coordination compounds represented by the above formulas III (1) to III (6), 50

In view of this, it is preferable that the metal coordination compound is represented by the formula III (2) or III (5).

Metal coordination compound represented by the formula III (1) ~III (6) , B is, in view of the blue emission color can be obtained> C == 〇 or> it is rather preferable is SO _2, From the viewpoint that emission wavelengths from green to red can be obtained,> 好ましい,> S or> CR ₂ is preferable.

The metal coordination compounds represented by the above formulas III (1) to ΠΙ (6) change the energy level of the lowest excited state by changing the substituent variously, and are used as a light emitting material of an organic EL having blue to red emission. Are suitable.

Specific examples of the metal coordination compounds represented by the formulas III (1) to (6) are shown below, but are not limited thereto. Incidentally, Table ΙΠ in one 1 Xi~X ₄ represents a substituent of the ring Alpha.

Table in-1

: The combination of metal coordination compounds represented by formulas 111 (1) to ΙΠ (6)

51/1

52

52/1

2β 53

2β

TA9

990lll / tO0 £ OAV 54

2β 54/1

2β 55

2β 55/1

56

Two 56/1

2β 57

2β 57/1

2β 58

2β 58/1

2β 59

2β 59/1

2β 60

60/1

2β 61

61/1

62

2β 62/1

2β 63

63/1

2β 64

2β 64/1

2β 65

65/1

66

66/1

The metal coordination compound of the present invention can be used as a material for an active layer of an electroluminescence device. Active layer means that the layer is capable of emitting light upon application of an electric field (light emitting layer) or that improves charge injection or charge transfer (charge injection layer or charge transfer layer). Here, charge refers to negative or positive charge. The thickness of the active layer is preferably from 10 to 100 nm, more preferably from 20 to 60 nm, and still more preferably from 20 to 40 nm.

The metal coordination compound of the present invention may be used as a mixture with other materials.The electroluminescent device using the metal coordination compound of the present invention may be made of a material other than the above metal coordination compound. Layer containing the metal coordination compound of the present invention.

67

It may be laminated with an active layer containing a substance. Materials that may be used in combination with the metal coordination compound of the present invention include known materials such as hole injection and / or hole transfer materials, electron injection and / or electron transfer materials, luminescent materials, and binder polymers. Things can be used. The material to be mixed may be a high-molecular material or a low-molecular material.

Materials that can be used for hole injection and / or hole transport materials include arylamine derivatives, triphenylmethane derivatives, stilbene compounds, hydrazone compounds, carbazole compounds, high molecular weight arylamine, polyaniline, polythiophene, etc. And materials obtained by polymerizing them. Those that can be used for electron injection and Z or electron transfer materials include oxaziazole derivatives, benzoxazole derivatives, benzoquinone derivatives, quinoline derivatives, quinoxaline derivatives, thiadiazol derivatives, benzodiazole derivatives, triazole derivatives, and metal chelate complexes. Materials such as compounds and the like and materials obtained by polymerizing them are exemplified. Materials that can be used for the light emitting material include arylamine derivatives, oxaziazole derivatives, perylene derivatives, quinacridone derivatives, pyrazoline derivatives, anthracene derivatives, rubrene derivatives, stilbene derivatives, coumarin derivatives, naphthylene derivatives, and metal chelates. Materials such as complexes, metal complexes containing central metals such as Ir and Pt, and materials obtained by polymerizing them, polymer materials such as polyfluorene derivatives, polyphenylenevinylene derivatives, polyphenylene derivatives, and polythiophene derivatives Is exemplified. Any binder can be used as long as it does not significantly reduce the properties. Examples of the binder polymer include materials such as polystyrene, polycarbonate, polyarylether, polyacrylate, polymethacrylate, and polysiloxane.

Among them, in the present invention, the above-mentioned metal coordination compound, and if necessary, 68

An organic electroluminescent device can be manufactured using a low-molecular material outside.

Specific examples of the low molecular weight material include CBP (4, 4'-N, N'-dicarbazole-biphenyl), CDBP (2, 2'-dimethyl-4, 4'-N, '-dicarbazol e-biphenyl) , M CP (m-dicarbazole-benzene) and the like. The mixing ratio of the low-molecular material and the metal coordination compound is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, and still more preferably 3 to 5% by weight of the low-molecular material. It is 8% by weight. If the concentration of the metal coordination compound is too low, the luminous efficiency tends to decrease. If it is too high, the concentration quenching occurs due to the interaction between the metal coordination compounds, and the luminous efficiency tends to decrease.

Further, in the present invention, an organic electroluminescence device can be manufactured using the above-mentioned metal coordination compound and a polymer composition containing a conjugated and / or non-conjugated polymer. In the present invention, the polymer composition is a composition obtained by mixing the above-mentioned metal coordination compound with a conjugated or Z- or non-conjugated polymer, or a conjugated and / or non-conjugated with the above-mentioned metal coordination compound. A composition obtained by copolymerizing with a polymer.

Specific examples of the conjugated and Z or non-conjugated polymers include, as a main skeleton, a structure of polyfluorene, polyphenylene, poly (phenylenevinylene), polythiophene, polyquinoline, polyaniline, polyvinylcarbazole, or a derivative thereof.ポリマー -containing polymer, as a unit (that is, not only the structure in the main skeleton, but also the side chain structure), benzene, naphthalene, anthracene, phenanthrene, chrysene, rubrene, pyrene, perylene, indene, Azulene, adamantane, fluorene, fluorenone, dibenzofuran, kytrazole, dibenzothiophene, furan, pyrrole, pyrroline, pyrrolidine, thiophene, dioxolan, pyrazole, pyrazoline, pyrazolidine, imidazole, 69

Oxazole, thiazole, oxazine diazole, triazole, thiadiazol, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, pyrazine, pyrazine, triazine, trithiane, norpolnen, benzofuran, indole, benzothiodazole, benzothiomizole, benzothiomizole, benzothiomizole, benzothiomizol , Benzothiazole, benzoxadiazole, benzotriazole, purine, quinoline, isoquinoline, coumarin, sinoline, quinoxaline, acridine, phenanthone, phenothiazine, flavone, triphenylamine, .acetylacetone, dibenzoylmethane , Picolinic acid, silyl, porphyrin and the like or a polymer containing the structure of a derivative thereof. The mixing or copolymerization ratio of the polymer and the metal coordination compound is preferably from 0.1 to 20 parts by weight of the polymer to 100 parts by weight. Solvents used in the polymer composition include chloroform form, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, anisol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl acetate solvent acetate, and the like. Can be used.

In order to use the metal coordination compound or the polymer composition of the present invention as an active layer material of an electroluminescence device, a method known to those skilled in the art, for example, vacuum evaporation, inkjet, casting, dipping, printing or This can be achieved by laminating a thin film on a substrate using spin coating or the like. Printing methods include letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reversal offset printing, screen printing, and gravure printing. Such a lamination method can usually be carried out in a temperature range of 120 to 130, preferably 10 to 100, particularly preferably 15 to 50 ° C. In addition, drying of the laminated polymer solution can be usually performed by drying at room temperature or by heating and drying using a hot plate. 70

Electroluminescent devices typically include an electroluminescent layer (light-emitting layer) between a force source and an anode, where at least one of the electrodes is transparent. In addition, one or more electron injection layers and Z or electron transfer layers can be inserted between the electroluminescent layer (light emitting layer) and the force sword, and one or more hole injection layers. A layer and a hole or hole transport layer can be inserted between the electroluminescent layer (light emitting layer) and the anode. The force sword material is preferably, for example, a metal or metal alloy such as Li, Ca, Mg, A1, In, Cs, Mg / Ag, and LiF. As the anode material, a metal (for example, Au) or another material having metal conductivity, for example, an oxide (for example, ITO: indium tin oxide) may be used on a transparent substrate (for example, glass or a transparent polymer). Can also be used.

The electron injection and Z or electron transfer layer include a layer containing a material such as an oxaziazole derivative, a benzoxazole derivative, a benzoquinone derivative, a quinoline derivative, a quinoxaline derivative, a thiadiazole derivative, a benzodiazole derivative, a triazole derivative, or a metal chelate complex compound. Can be

For hole injection and Z or hole transport layer, copper phthalocyanine, triphenylamine derivative, triphenylmethane derivative, stilbene compound, hydrazone compound, carbazole compound, high molecular weight arylamine, polyaniline, polythiophene, And the like.

The metal coordination compound of the present invention is suitable, for example, as a material for an organic EL device having various emission wavelengths and excellent in reliability, emission characteristics, and the like. Among them, the metal coordination compounds represented by the formulas I (1) to 1 (6) are effective for shortening the emission wavelength, and the metal coordination compounds represented by the formulas II (1) to 11 (6) The compounds are effective in extending the lifetime of the device, and the metal coordination compounds represented by the formulas III (1) to III (6) are effective in shortening the emission color and extending the lifetime of the device. 71

Example

The present invention will be described with reference to the following examples, but the present invention is not limited to these examples. In addition, in addition to the examples described below, even when the above-described various metal coordination compounds of the present invention are used, an electroluminin sense element having excellent color purity, excellent reliability, excellent light emitting characteristics, and the like can be obtained. Can be.

Example I Synthesis of 1 1 metal coordination compound 1 (1)

A THF solution of 3-bromo-9-methylcarbazole (3 Ommo 1) was gradually added to a THF mixture of magnesium (1.9 g, 8 Ommo 1) under a stream of argon with good stirring, and the Grignard reagent was added. Was prepared. The resulting Darynal reagent was gradually added dropwise to a THF solution of trimethyl borate ester (30 Ommo 1) at 178 ° C over 2 hours while being stirred well, and then stirred at room temperature for 2 days. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. The obtained aqueous solution was extracted with toluene, and the extract was concentrated to give a colorless solid. The solid obtained was recrystallized from toluene / acetone (1 ノ 2) to give the borazole derivative boronic acid as colorless crystals (40%). The obtained carpazole derivative boronic acid (12 mmo 1) and 1,2-ethanediol (3 Ommo 1) were refluxed in toluene for 10 hours, and then recrystallized from toluene / acetone (1Z4). The rubazole derivative boron ester was obtained as colorless crystals.

2-bromopyridine (1 Ommo 1), boron ester derivative of boron 72

(10 mm o 1), a toluene solution of _{P d (0) (PPh 3} ) 4 (0. 2mmo 1), under argon, the K ₂ C0 ₃ aqueous 2M was added, stirred vigorously products et 48 hours Refluxed. After the reaction mixture was cooled to room temperature, it was poured into a large amount of methanol to precipitate a solid. The precipitated solid was filtered by suction and washed with methanol to obtain a solid of 3- (2′-pyridyl) -19-methylcarbazole.

Iridium chloride (III) (1.7 mmo 1), 3- (2'-pyridyl) -1 9-methylcarbazolyl (7.58 mmo 1), ethoxyethanol 50 m 1 and water in a 20 Om 1 three-necked flask 20 ml was added, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes, and then stirred under reflux for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and then washed sequentially with ethanol and acetone. Dried under reduced pressure at room temperature, di-chloro over tetrakis [3- (2, - pyridyl) Single 9-1 methylcarbamate Eaux Le one N ¹ ', C ^2] to give a pale yellow powder diiridium (III).

73

In a 200 ml three-necked flask, 70 ml of ethoxyethanol, di-chlorotetrakis [3- (2'-pyridyl) -9-methylcarbazolyl, C ² ] diiridium (III) (0.7 mmo 1), Acetyl acetone (2.1 lmmol) and sodium carbonate (9.43 mmol) were added, and the mixture was stirred at room temperature under a nitrogen stream, and then refluxed for 15 hours. The reaction was cooled on ice, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: Black hole Holm / main evening Nord: 30Z1) to give bis [3- (2 'single-pyridyl) one 9-methyl carbazole Ichiru - lambda ^', C ² 1 (Acetylacetonato) A pale yellow powder of iridium (III) was obtained.

The obtained compound was confirmed by NMR spectrum, IR spectrum and the like. The same applies to the compounds shown below.

74

Example I Synthesis of 1-2 Metal Coordination Compound I (2)

3- (2′-Pyridyl) -9-methylcarbazole (1.7 mmol) in a 200-ml three-necked flask, bis [3- (2′-pyridyl) -1-synthesized in Example I-1 9-Methylcarbazole-iV, C ² ] (acetylacetonato) iridium (III) (0.28 mmo 1) and 55 ml of glycerol were added, and the mixture was heated and stirred at about 180 ° C. for 8 hours under a nitrogen stream. The reaction product was cooled to room temperature, poured into 350 ml of 1N hydrochloric acid, and the precipitate was collected by filtration, washed with water, and dried under reduced pressure at 100 ° C for 5 hours. The precipitate was purified black port Holm in eluent and the silica force gel column chromatography, tris [3- (2 'single-pyridyl) Single 9 Mechirukarubazo Ichiru - lambda ^', C ² 1 iridium (III) A pale yellow powder was obtained.

75

Examples I-13 to I-19 Synthesis of Various Metal Coordination Compounds

As shown in Table I-12 below, the synthesis was performed in the same manner as in Example I-11 and Example I-12 except that the starting materials such as the sorbazole unit, ring A, and other ligands were changed. Various metal complex compounds were synthesized.

Table I — 2

76/1

Paper (Rule 2β) 76/2

Example I-10 Preparation of Organic EL Device

Using the compound obtained in Example I-12, an organic EL device having three organic layers was produced, and the device characteristics were evaluated.

I TO and (indium tin oxide) glass substrate was patterned into a 2mm width, an NPD shed as a hole transport layer by a vacuum evaporation method by resistance heating in a vacuum chamber within one 10_ ⁵ P a, thickness 40 nm was formed. Further, the metal coordination compound of Example I-2 was co-deposited with CBP at a weight ratio of 5% (film thickness: 30 nm). Further, 30 nm of A 1 Q ₃ was deposited as an electron transport layer. On this, as a cathode electrode layer, LiF is 0.5 to 2 nm and A1 is 100 to 150 nm.

Replacement paper (Rule 2β) 77

Evaporated.

The characteristics of the organic EL device were measured at room temperature, the current-voltage characteristics were measured with a micro-ammeter 4140 B manufactured by Hewlett-Packard Company, and the emission luminance was measured with SR-3 manufactured by Topcon. When voltage was applied using ITO as the anode and LiF / A1 as the cathode, blue light emission (λ = 450 nm) was observed at about 6 V.

The luminance half-life when driven at a constant current (50 mAZcm ² ) was 100 hours.

Comparative Example 1

An organic EL device was fabricated in the same manner as in Examples 1 to 10, except that Ir (ppy) ₃ was used instead of the metal coordination compound used in Example I-10. When the obtained device was connected to a power supply and a voltage was applied using ITO as the anode and LiF / A1 as the cathode, green light emission (λ == 516 nm) was observed at about 6 V.

When the luminance half-life when driven at a constant current (50 mAZcm ² ) was measured, it was 80 hours.

Example II Synthesis of one-metal coordination compound II (1)

In a THF mixture of magnesium (1.9 g, 8 Ommo 1), a THF solution of 2-hydroxy 6-bromo-9-methylcarbazolyl (3 Ommo 1) was gradually added with good stirring under an argon stream. A Grignard reagent was prepared. The resulting Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (30 Ommo 1) at −78 ° C. over 2 hours while being stirred well, and then stirred at room temperature for 2 days. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. The resulting aqueous solution was extracted with toluene, and the extract was concentrated to give a colorless solid. The solid obtained was recrystallized from toluene / acetone (1Z2) to give the borazole derivative boronic acid as colorless crystals (40%). 78

The obtained carpazole derivative boronic acid (12 mmo 1) and 1,2-ethanediol (30 mmol) were refluxed in toluene for 10 hours, and then recrystallized from toluene / acetone (1Z4). The ester was obtained as colorless crystals.

2M K ₂ C〇 in a toluene solution of 2-bromopyridine (1 Ommo 1), carbazole derivative boron ester (1 Ommo 1), Pd (0) (PPh ₃ ) ₄ (0.2 mmo 1) under an argon stream ₃ Aqueous solution was added and refluxed for 48 hours with vigorous stirring. After the reaction mixture was cooled to room temperature, it was poured into a large amount of methanol to precipitate a solid. The precipitated solid was filtered by suction and washed with methanol to obtain 2-hydroxy-16- (2'-pyridyl) -19-methylcarbazole solid.

Iridium chloride (III) (1.7 mmol), 2-hydroxy-6- (2'-pyridyl) -19-methylcarbazole (7.58 mmo1), ethoxyethanol 5 Oml in a three-neck flask with 20 Om 1 And 2 Oml of water 79

The mixture was stirred at room temperature under flowing water for 30 minutes, and then stirred under reflux for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and washed sequentially with ethanol and acetone. Dried under reduced pressure at room temperature, di - chloro over tetrakis [2- hydroxy-6- (2, - pyridyl) Single 9-1 methylcarbazole -Α ^ ', C ^7] to give a pale yellow powder diiridium (III).

Ethoxyethanol 7 Om 1 three-neck flask 200 ml, di one - black Rotetorakisu [2-hydroxy-6- (2 '- pyridyl) -9 one Mechirukaru Vazo one Roux V ^J', C ⁷ 1 diiridium ( III) (0.7 mmo 1), acetyl acetone (2.1 Ommo 1) and sodium carbonate (9.43 mmo 1) were added, and the mixture was stirred at room temperature under a nitrogen stream, and then stirred under reflux for 15 hours. The reaction was cooled on ice, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: chloroform / methanol: 30Z1) to give bis [2-hydroxy-one 6- (2 '- pyridyl) one 9-methyl carbazole - lambda ^', C ^7] ( (Acetyl acetonato) A pale yellow powder of iridium (III) was obtained. 80

Example II Synthesis of 1-2 Metal Coordination Compound II (2)

2-hydroxy-16- (2'-pyridyl) -19-methylcarbazole (1.7 mmo1) in a 200 ml three-necked flask, bis [2-hydroxy-6-) synthesized in Example II-11 (2 '- pyridyl) one 9-methyl carbazole over V ^J', C ^7] put (§ cetyl § Setona g) iridium (III) and (0. 2 8Mmo 1) glycerol 5 5 m l, about a nitrogen stream 1 The mixture was heated with stirring at 80 for 8 hours. The reaction product was cooled to room temperature, poured into 35 Nm of 1N-hydrochloric acid, and the precipitate was collected by filtration, washed with water, and dried under reduced pressure at 100 ° C for 5 hours. The precipitate was purified by silica gel column chromatography using chloroform as eluent, and the pale yellow color of tris [2-hydroxy-6- (2′-pyridyl) -19-methylcarbazo-l-Λ ^ ', OH iridium (III) A powder was obtained. 81

Examples 11-3 to 11-3 Synthesis of Various Metal Coordination Compounds

As shown in Table II-12 below, the synthesis method of Examples II-11 and II-12 was used except that the starting materials such as the sorbazole unit, ring A, and other ligands were changed. Various metal complex compounds were synthesized.

82

(Rule 26)

1 / Z2

J6 £ 800 / 00Zdf / X3d 990 so-called OAV 82/2

Example II-14 Fabrication of Organic EL Device

Example 11 Using the compound obtained in 1-2, an organic EL device having three organic layers was fabricated.

Replacement paper (Rule 2β) 83

Then, the device characteristics were evaluated.

I TO and (indium tin oxide) glass substrate was patterned into a 2mm width, a a- NPD as a hole transport layer by a vacuum evaporation method by resistance heating in a vacuum chamber within one 10- ⁵ P a, film A thickness of 40 nm was formed. Further, the metal coordination compound of Example II-12 was co-deposited with CBP so that the weight ratio was 5% (film thickness: 30 nm). Further, 30 nm of A 1 Q ₃ was deposited as an electron transport layer. On this, 0.5 to 2 nm of LiF and 100 to 150 nm of A1 were deposited as a cathode electrode layer.

The characteristics of the organic EL device were measured at room temperature, the current-voltage characteristics were measured with a micro-electrometer 4140B manufactured by Hewlett-Packard Company, and the emission luminance was measured with SR-3 manufactured by Topcon. When voltage was applied using IT〇 as the anode and Li FZA 1 as the cathode, orange emission (λ = 59 Onm) was observed at about 6 V.

The luminance half-life measured at a constant current (50 mA / cm ² ) was 200 hours.

Example III Synthesis of 1 1 Metal Coordination Compound III (1)

A Grignard reagent was prepared by gradually adding a THF solution of 2-bromo-9-fluorenone (3 Ommo 1) to a THF mixture of magnesium (1.9 g, 8 Ommo 1) while stirring well under a stream of argon. . The obtained Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (30 Ommo 1) over 2 hours while stirring well at −78 ° C., followed by stirring at room temperature for 2 days. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. The obtained aqueous solution was extracted with toluene, and the extract was concentrated to give a colorless solid. By recrystallizing the obtained solid from toluenenoacetone (1/2), the fluorenone derivative boronic acid was obtained as colorless crystals (40%). The obtained fluorenone derivative boronic acid (12mmo 1) and 1,2-ethanediol 84

(3 Ommo 1) was refluxed in toluene for 10 hours and then recrystallized from toluene / acetone (1/4) to obtain a fluorenone derivative boron ester as colorless crystals.

2-bromopyridine. (1 Ommo 1), fluorenone derivative boron ester (1 Ommo 1), Pd (0) (PP ₃ ) ₄ (0.2 mmo 1) in toluene solution under argon atmosphere, 2M K ₂ C0 ₃ solution was added, vigorously while stirring was refluxed et 48 hours. After the reaction mixture was cooled to room temperature, it was poured into a large amount of methanol to precipitate a solid. The precipitated solid was filtered by suction and washed with methanol to obtain a solid of 2- (2′-pyridyl) -19-fluorenone.

Iridium chloride (III) (1.7 mmol), 2- (2,1-pyridyl) _9-fluorenone (7.58 mmo1), ethoxyethanol 5 Om1 and water 2 Om in a three-neck flask of 20 Om1 1 and stirred at room temperature under a nitrogen stream for 30 minutes, and then stirred under reflux for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and washed sequentially with ethanol and acetone. Dried under reduced pressure at room temperature, di - A chloro over tetrakis [2- (2 'single-pyridyl) Single 9 one Furuorenon one A ^', C ^5] to give a pale yellow powder diiridium (III). 85

Ethoxyethanol 70m 1 three-neck flask 200 ml, di one - black Rotetorakisu [2- (2, single-pyridyl) Single 9- Furuorenon one lambda ^ ', C ^3] diiridium (III) (0. 7 mm 0 1), acetylacetone (2.1 Ommo 1) and sodium carbonate (9.43 mmo 1) were added, and the mixture was stirred at room temperature under a nitrogen stream, and then stirred under reflux for 15 hours. The reaction was cooled on ice, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: formaldehyde methanol: 30/1), and bis [2- (2, -pyridyl) -19-fluorenone-N ¹ ', C ³ ] (acetyl (Acetonato) A pale yellow powder of iridium (III) was obtained.

Example ΠΙ—Synthesis of metal coordination compound III (2) 86

2- (2,1-pyridyl) -19-fluorenone (1.7 mmo 1) in a 200-ml three-necked flask, bis [2- (2'-pyridyl)-9-fluorenone synthesized in Example III-1 {^ ', C ³ ] (acetylacetonato) Iridium (III) (0.28 mmo 1) and 55 ml of glycerol were added, and the mixture was heated and stirred at about 180 ° C. for 8 hours under a nitrogen stream. The reaction was cooled to room temperature, poured into 1N hydrochloric acid (35 Om1), and the precipitate was collected by filtration, washed with water, and dried under reduced pressure at 100 ° C for 5 hours. The precipitate was purified by silica gel column chromatography using a chromatographic form as the eluent.

[2— (2′-pyridyl) -1-9-fluorenone-1 A ′, C ³ ] A light yellow powder of iridium (III) was obtained.

Example III-1 3 to Example III-1 17

Except that the starting materials such as the condensed ring unit, ring A, and other ligands were changed, a method similar to that of the synthesis method of Example III-1 and Example III-2 was used, as shown in Table III-12 below. Various metal complex compounds were synthesized. ' 87

(Rule 26) 87/1

(Rule 26) 88

Paper (Rule 2β) 88/1

Example III-18 Fabrication of organic EL device

Using the compound obtained in Example III-12, an organic EL device having three organic layers was produced, and the device characteristics were evaluated.

I TO and (indium tin oxide) glass substrate was patterned into a 2mm width, a a- NPD as a hole transport layer by a vacuum evaporation method by resistance heating in a vacuum chamber within one 10- ⁵ P a, film A thickness of 40 nm was formed. Further, the metal coordination compound of Example III-2 was co-deposited with CBP at a weight ratio of 5% (thickness: 30 nm). Further, 30 nm of Al Q ₃ was deposited as an electron transport layer. On this, as a cathode electrode layer, LiF was 0.5 to 2 nm and Al was 100 to 150 nm.

The characteristics of the organic EL device were measured at room temperature. When voltage was applied using ITO as the anode and Li FZA1 as the cathode, blue light emission (λ = 450 nm) was observed at about 6 V.

Paper (Rule 2β)

Claims

89 A claim A metal coordination compound represented by any one of formulas (1) to (6).

(one two Three)

B:>N,>0,>S,> C = 0,> S〇 ₂ ,> CR

Wherein M is Ir, Rh, Ru, 〇s, Pd or Pt, and n is 2 or 3. M is Ir, Rh, Ru or 〇s and n is 2 In this case, another bidentate ligand is bonded to M. Ring A is a cyclic compound containing a nitrogen atom bonded to M. Xi Xe and R are each independently — R —〇R ² , — SR ³ , 90

— OCOR ⁴ , one CO〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , and —NR ⁹ R ¹⁰ (where ¹ to! ^ ¹ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbon number 1 to 22 straight-chain, cyclic or branched alkyl groups or halogen-substituted alkyl groups in which part or all of the hydrogen atoms are substituted with halogen atoms, aryl groups having 6 to 21 carbon atoms A heteroaryl group having 2 to 20 carbon atoms or an aralkyl group having 7 to 21 carbon atoms, or a halogen-substituted aryl group or a halogen-substituted heteroaryl group in which some or all of the hydrogen atoms have been replaced with halogen atoms. , Represents a halogen-substituted aralkyl group, and ¹ to! ^ ¹¹⁵ may be the same or different.) And Xi to X ₆ are the same. and or different, ring A is defined by Xi～X ₆ May have the same substituent as the above group. )

2. The metal coordination compound according to claim 1, represented by any one of formulas (1) to (6).

91

I-(1) I- (2) I- (3)

I-(4) I-(5) I- (6)

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or Os and n is 2, Another bidentate ligand is bonded to M. Ring A is a cyclic compound containing a nitrogen atom bonded to M. 〜 to? Are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a charcoal. A straight-chain, cyclic or branched alkyl group having 1 to 22 primes or a halogen-substituted alkyl group in which part or all of the hydrogen atoms thereof have been substituted with a hapogen atom; an aryl group having 6 to 21 carbon atoms; A halogen-substituted aryl group, a halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, a halogen-substituted aralkyl group having 2 to 20 heteroaryl groups or an aralkyl group having 7 to 21 carbon atoms or a hydrogen atom partially or wholly substituted with a halogen atom; may be any of groups, also, Xi～X ₇ is 92

It may be one or different, and ring A may have the same substituent as the group defined by X _{1 to} X ₇ . )

3. In the above formulas I (1) to 1 (6), ring A may have the same substituent as the group defined by a, pyridine, quinoline, benzoxazole, benzothiazole, benzo 3. The metal coordination compound according to claim 2, which is imidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazol, triazole, benzopyrazole or triazine. '

4. X _{1 to} X ₇ in the above formulas I (1) to 1 (6) or at least one of the substituents defined in the same manner as Xi Xy in the ring A is a fluorine atom or a trifluoro group. 4. The metal coordination compound according to claim 2, which is a methyl group.

5. The metal coordination compound according to claim 1, represented by any one of formulas II (1) to Π (6).

93

II- (l) 11- (2) 11- (3)

11- (4) 11- (5) II- (6)

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. M is Ir, Rh, Ru or 〇s, and n is 2 In this case, another bidentate ligand is bonded to M. Ring A is a cyclic compound containing a nitrogen atom bonded to M. Xi X? Are each independently — H, -OH, -RK -OR ² , ―

SR ³ , one COR ⁴ , one CO〇R ⁵ , one Si R ⁶ R ⁷ R ⁸ , one NH ₂ , one NHR 9

, And —NR ^ R ¹¹ (where R ¹ ! ^ ¹¹ is a straight-chain, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, and 2 to 20 carbon atoms) A heteroaryl group or an aralkyl group having 7 to 21 carbon atoms, wherein R ^{1 to} R n may be the same or different.) A substituent selected from the group consisting of X _{t to} X ₇ may be the same or different 94

Well, ring A may have the same substituent groups as defined in X to X _7. )

6. In the above formulas II (1) to 11 (6), ring A may have the same substituent as the group defined by pyridine, quinoline, benzoxazole, benzothiazole, benzo 6. The metal coordination compound according to claim 5, which is imidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazol, triazole, benzopyrazole, triazine or isoquinoline.

7. The metal coordination compound according to claim 1, which is represented by any one of formulas III (1) to ((6).

95

III-(1) ΙΠ- (2) 111- (3)

111- (4) III- (5) III- (6)

B:>0,> S, > C = O,> S0 2,> CR,

(Where M is Ir, Rh, Ru, Os, Pd or Pt, and n is 2 or 3. When M is Ir, Rh, Ru or 〇s and n is 2 And another bidentate ligand is bound to M. Ring A is a cyclic compound containing a nitrogen atom bound to M. Xi Xe and R are each independently — R -OR ² , — SR ³ , 100 COR ⁴ , —CO〇R ⁵ , 1 Si R ⁶ R ⁷ R ⁸ , and — NR ⁹ R ¹⁰ (However,! ^ ~ ¹ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, A straight-chain, cyclic or branched alkyl group having 1 to 22 carbon atoms or a halogen-substituted alkyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms; 96

An aryl group having 2 to 20 carbon atoms or an aralkyl group having 7 to 21 carbon atoms, or a halgen-substituted aryl group in which part or all of the hydrogen atoms thereof have been replaced with halgen atoms; · Halogen-substituted heteroaryl group and halogen-substituted aralkyl group. ^ ¹ ~! ^ ¹ . May be the same or different. Xi Xe may be the same or different, and ring A has the same substituent as the group defined by Xi Xe May be. )

8. In the above formulas III (1) to III (6), ring A may have the same substituent as the group defined by Xi Xe, pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole 8. The metal coordination compound according to claim 7, which is benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole, triazine or isoquinoline.

9. The metal coordination compound according to any one of claims 1 to 8, wherein M is Ir.

10. A polymer composition comprising a metal coordination compound according to any of claims 1 to 9, and conjugated and Z or non-conjugated polymers.

11. An organic electroluminescent device produced using the metal coordination compound according to any one of claims 1 to 9, or the polymer composition according to claim 10.