JP2001247859A - Luminescent element material comprising ortho metallized iridium complex, luminescent element and novel iridium complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luminescent element having excellent luminescence properties and a material for preparing the same. SOLUTION: The luminescent element material comprises an ortho metallized iridium complex having a partial structure of formulae 1, 2 or 3 (wherein R1 and R2 are each a substituent; q1 and q2 are each an integer of 0-4; and q1+q2 is >=1) or its tautomer. Specific examples are the compounds of formulae 1-3, 1-1 and 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting element material and a light emitting element capable of emitting light by converting electric energy into light, and relates to a display element, a display, a backlight, an electrophotograph, an illumination light source, a recording light source, an exposure light source, Reading light source,
The present invention relates to a light-emitting element that can be suitably used in fields such as signs, signboards, and interiors. In addition, the present invention relates to a novel light emitting material expected to be applied in various fields.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active. Among them, an organic electroluminescence (EL) element has been attracting attention as a promising display element because it can emit light with high luminance at a low voltage. ing. For example, a light emitting device that forms an organic thin film by vapor deposition of an organic compound is known (Applied Physics Letters, Vol. 51, No. 91).
3, 1987). The light-emitting element described in this document uses a tris (8-hydroxyquinolinato) aluminum complex (Alq) as an electron transporting material and is laminated with a hole transporting material (amine compound) to form a conventional single-layered device. Compared with this, the light emission characteristics are greatly improved.

In recent years, the application of organic EL elements to color displays has been actively studied, but in order to develop high-performance color displays, the characteristics of the light emitting elements of blue, green, and red are improved. There is a need.

As a means for improving the characteristics of light emitting devices, an orthometalated iridium complex (Ir (ppy) ₃ : Tris-Orth
o-Metalated Complex of Iri
dium (III) with 2-Phenylpyr
and a green light-emitting device utilizing light emission from the luminescent line (Applied Physics Letters 75, 4 (19)).
99). ). This device has achieved an external quantum yield of 8%,
Although it exceeds the external quantum yield of 5%, which has been said to be the limit of conventional devices, it is limited to green light emission, so its application range as a display is narrow, and light emitting device materials that emit light of other colors with high efficiency are considered. Development was required.

On the other hand, organic light-emitting devices that achieve high-luminance light emission are devices in which organic substances are stacked by vacuum deposition. However, from the viewpoints of simplification of the manufacturing process, workability, and large area, etc. It is desirable to produce the element by a coating method.
However, a device manufactured by a conventional coating method is inferior to a device manufactured by a vapor deposition method, particularly in terms of luminous efficiency.
Development of a new light emitting element material has been desired. In recent years,
A variety of fluorescent substances are used in filter dyes, color conversion filters, photographic light-sensitive material dyes, sensitizing dyes, pulp dyes, laser dyes, fluorescent materials for medical diagnosis, materials for organic light-emitting devices, and the like. There is a growing demand for new light-emitting materials.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light emitting device having good light emitting characteristics, a material for the light emitting device enabling the light emitting device, and a new light emitting material usable in various fields.

[0007]

This object has been achieved by the following means. 1. A light emitting device material comprising a compound having a partial structure represented by the general formula (1) or a tautomer thereof.

[0008]

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[0009] 2. A light emitting device material comprising a compound having a partial structure represented by the general formula (2) or a tautomer thereof.

[0010]

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3. A light emitting device material comprising a compound having a partial structure represented by the general formula (3) or a tautomer thereof.

[0012]

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In the formula, R ¹ and R ² each represent a substituent.
q ¹ and q ^{2 each} represent an integer of 0 to 4, and q ¹ + q ² represents 1
That is all.

4. A compound having a partial structure represented by the general formula (4) or a tautomer thereof.

[0015]

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In the formula, Z ¹¹ and Z ¹² each represent a nonmetallic atomic group necessary for forming a 5- or 6-membered ring together with a carbon atom and / or a nitrogen atom, and this ring has a substituent. And a condensed ring with another ring may be formed. Ln ¹ represents a divalent group. Y ¹ represents a nitrogen atom or a carbon atom, and b ¹ represents a single bond or a double bond.

5. A luminescent material comprising the compound described in 4 above.

6. A light emitting material comprising a compound having a partial structure represented by the general formula (5).

[0019]

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[7] FIG. A light emitting material comprising a compound having a partial structure represented by the general formula (6).

[0021]

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8. A light emitting material comprising a compound having a partial structure represented by the general formula (7) or a tautomer thereof.

[0023]

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In the formula, Z ²¹ and Z ²² each represent a nonmetallic atomic group necessary for forming a 5- or 6-membered ring together with a carbon atom and / or a nitrogen atom, and this ring has a substituent. And may form a condensed ring with another ring. Y ² represents a nitrogen atom or a carbon atom, and b ² represents a single bond or a double bond.

9. A light emitting material comprising a compound having a partial structure represented by the general formula (8) or a tautomer thereof.

[0026]

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Wherein X ²⁰¹ , X ²⁰² , X ²⁰³ and X
²⁰⁴ represents a nitrogen atom or C—R, forms a nitrogen-containing heteroaryl 6-membered ring together with —C ＝ N—, X ²⁰¹ , X
^At least one of ²⁰² , X ²⁰³ and X ²⁰⁴ represents a nitrogen atom. R represents a hydrogen atom or a substituent. Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring. 10. A light emitting material comprising a compound having a partial structure represented by the general formula (9) or a tautomer thereof.

[0028]

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In the formula, Z ²⁰¹ and Z ³⁰¹ each represent an atomic group forming an aryl ring or a heteroaryl ring. 11. A light emitting material comprising a compound having a partial structure represented by the general formula (10) or a tautomer thereof.

[0030]

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In the formula, Z ²⁰¹ and Z ⁴⁰¹ each represent an atomic group forming an aryl ring or a heteroaryl ring. 12. 12. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer are formed between a pair of electrodes, wherein at least one of the light-emitting elements contains the light-emitting material described in any one of the above items 1, 2, 3, 5 to 11. 13. In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes,
12. An organic light-emitting device comprising at least one layer consisting of the light-emitting material described in 2, 3, 5 to 11 alone. 14． In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, a coating process in which at least one layer includes an orthometallated iridium complex and includes a layer including the orthometalated iridium complex. A light-emitting element characterized in that a film is formed by:

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound of the present invention is a light emitting device material composed of orthometalated iridium complexes. The orthometalated metal complex is described, for example, in "Organic Metal Chemistry-Fundamentals and Applications-", p.
Published by Akio Yamamoto in 1982, Photochemistry and Ph
otophysics of Coordination Compounds '' p71-p77, p13
5-p146 A generic term for a group of compounds described in Springer-Verlag Company, H. Yersin, published in 1987.

The valence of iridium in the orthometalated iridium complex is not particularly limited, but is preferably trivalent. The ligand of the ortho-metalated iridium complex is not particularly limited as long as it can form an ortho-metalated complex. For example, an aryl-substituted nitrogen-containing heterocyclic derivative (the aryl group is substituted at the nitrogen-containing heterocyclic nitrogen On the carbon adjacent to the atom, examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Further, the aryl group may form a condensed ring with a carbocycle or a heterocycle.
Examples of the nitrogen-containing hetero ring include, for example, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline,
Quinoxaline, phthalazine, quinazoline, naphthodine, cinnoline, perimidine, phenanthroline, pyrrole, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiadiazole, benzimidazole, benzoxazole, benzothiazole, phenanthridine, etc.), heteroaryl Group-substituted nitrogen-containing heterocyclic derivative (the substitution position of the heteroaryl group is on the carbon adjacent to the nitrogen-containing heterocyclic nitrogen atom, and examples of the heteroaryl group include a group containing the above-mentioned nitrogen-containing heterocyclic derivative, a thienyl group, and a furyl Group, etc.), 7,8-benzoquinoline derivatives, phosphinoaryl derivatives, phosphinoheteroaryl derivatives, phosphinoxyaryl derivatives, phosphinoxyheteroaryl derivatives, amino Methyl aryl derivatives, aminomethyl heteroaryl derivatives. Aryl-substituted nitrogen-containing aromatic heterocyclic derivatives, heteroaryl-substituted nitrogen-containing aromatic heterocyclic derivatives, 7,8-benzoquinoline derivatives are preferred, and phenylpyridine derivatives,
Thienylpyridine derivatives, 7,8-benzoquinoline derivatives, benzylpyridine derivatives, phenylpyrazole derivatives, phenylisoquinoline derivatives, and phenyl-substituted derivatives of azoles having two or more nitrogen atoms are more preferable, and thienylpyridine derivatives, 7,8-benzoquinoline Particularly preferred are derivatives, benzylpyridine derivatives, phenylpyrazole derivatives, phenylisoquinoline derivatives, and phenyl-substituted derivatives of azoles having two or more nitrogen atoms.

The compound of the present invention may have other ligands in addition to the ligand necessary for forming an orthometalated complex. As other ligands, there are various known ligands, for example, “Photochemistry and Photophysics of
Coordination Compounds '' Springer-Verlag H. Yersi
n Published in 1987, "Organic Metal Chemistry-Fundamentals and Applications-"
The ligands described in Shokabosha, Akio Yamamoto, published in 1982, and the like, are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, bipyridyl, phenanthroline, etc.) ) And diketone ligands, more preferably chlorine ligands and bipyridyl ligands.

The compound of the present invention may have one kind of ligand or a plurality of kinds. The number of ligands in the complex is preferably one to three, particularly preferably one or two, and more preferably one.

The compound of the present invention preferably has 5 carbon atoms.
-100, more preferably 10-80, even more preferably 14-50.

Among the compounds having a partial structure represented by the general formulas (1) to (10) or tautomers thereof of the present invention, the compounds represented by the general formulas (1), (2), (4) to (10) A compound having a partial structure represented by or a tautomer thereof is more preferred.

The compound having a partial structure represented by the general formula (1) or a tautomer thereof may be a compound having one iridium atom in the compound or a so-called dinuclear complex having two or more iridium atoms. There may be. Other metal atoms may be simultaneously contained. The same applies to the compound having a partial structure represented by any of formulas (2) to (10) or a tautomer thereof.

In the general formula (3), R ¹ and R ² represent a substituent. q ¹ and q ^{2 each} represent an integer of 0 to 4, and q ¹ +
q ² is 1 or more. When q ¹ and q ² are 2 or more, a plurality of R ¹ and R ² may be the same or different from each other. As R ¹ and R ² , for example, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl group, pentafluoroethyl group, etc., and alkenyl group (preferably having 2 to 30 carbon atoms). More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 carbon atoms.
To 10, for example, vinyl, allyl, 2-butenyl,
3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 carbon atoms)
-20, particularly preferably 2-10 carbon atoms, such as propargyl and 3-pentynyl. ),
An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl,
And anthranil. ), An amino group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 20 carbon atoms,
Particularly preferably, it has 0 to 10 carbon atoms, for example, amino,
Methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino and the like can be mentioned. ), An alkoxy group (preferably having 1 carbon atom)
-30, more preferably 1-20 carbon atoms, particularly preferably 1-10 carbon atoms, such as methoxy, ethoxy,
Butoxy, 2-ethylhexyloxy and the like. ), An aryloxy group (preferably having 6 to 3 carbon atoms)
It has 0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, and 2-naphthyloxy. ), A heteroaryloxy group (preferably having 1 carbon atom)
-30, more preferably 1-20, particularly preferably 1-12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. ), An acyl group (preferably having 1 to 3 carbon atoms)
It has 0, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and includes, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl), and aryloxycarbonyl Group (preferably having 7 to 30 carbon atoms, more preferably having 7 carbon atoms)
-20, particularly preferably 7-12 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), and an acylamino group (preferably 2-3 carbon atoms
It has 0, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and includes, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonylamino and the like), aryloxycarbonylamino Group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), and a sulfonylamino group (preferably having a carbon number of 7). 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably 0-30 carbon atoms, More preferably 0 to 2 carbon atoms
0, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), Carbamoyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Number 6 to 30, more preferably carbon number 6 to 20,
Particularly preferably, it has 6 to 12 carbon atoms, such as phenylthio. ), A heteroarylthio group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 2 carbon atoms)
0, particularly preferably 1 to 12 carbon atoms, for example, pyridylthio, 2-benzimidolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. ), A sulfonyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. ), Sulfinyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 3 carbon atoms)
It has 0, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms
2, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, and the like. Can be ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 3 carbon atoms)
0, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl. ). These substituents may be further substituted. Further, R ¹ groups, R ² groups, or R ¹ and R ² groups may be bonded to form a condensed ring structure.

R ¹ and R ² are preferably an alkyl group, an aryl group, an alkoxy group, an amino group, a cyano group or a group forming a condensed ring structure by bonding, and an alkyl group forming a condensed aromatic ring structure by bonding. Are more preferred. q ¹ and q ² are 0, 1,
2 is preferable, and q ¹ + q ² = 1 or 2 is more preferable.

In the general formula (4), Z ¹¹ and Z ¹² each represent a nonmetallic atomic group necessary for forming a 5- or 6-membered ring, and this ring may have a substituent. Further, a condensed ring may be formed with another ring. Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, cyano, nitro, -OR ¹⁰¹ , -SR ¹⁰² , -CO
₂ R ¹⁰³ , -OCOR ¹⁰⁴ , -NR ¹⁰⁵ R ¹⁰⁶ , -CONR
_{^{107 R 108, -SO 2 R 10}} 9, -SO 2 NR 110 R 111, -N
R ¹¹² CONR ¹¹³ R ¹¹⁴ , -NR ¹¹⁵ CO ₂ R ¹¹⁶ , -CO
R ¹¹⁷ , -NR ¹¹⁸ COR ¹¹⁹ or -NR ¹²⁰ SO ₂ R ¹²¹
Is mentioned. Where R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R
¹⁰⁵ , ^R106 , ^R107 , ^R108 , ^R109 , ^R110 , ^R111 , R
¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R
¹¹⁹ , R ¹²⁰ and R ¹²¹ each independently represent a hydrogen atom,
It is an aliphatic group or an aryl group.

Examples of the substituent include a halogen atom,
Aliphatic group, aryl group, -OR ¹⁰¹ , -SR ¹⁰² , -NR
¹⁰⁵ R ¹⁰⁶ , -SO ₂ R ¹⁰⁹ , -NR ¹¹² CONR
¹¹³ R ¹¹⁴ , -NR ¹¹⁵ CO ₂ R ¹¹⁶ , -NR ¹¹⁸ COR ¹¹⁹
Or -NR ¹²⁰ SO ₂ R ¹²¹ , preferably a halogen atom, an aliphatic group, an aryl group, -OR ¹⁰¹ , -S
R ¹⁰² , —NR ¹⁰⁵ R ¹⁰⁶ or —SO ₂ R ¹⁰⁹ is more preferable, and a halogen atom, an alkyl group, an aryl group, an alkoxy group, a phenoxy group, or a dialkylamino group is more preferable; It is more preferably an alkyl group having 1 to 10 atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and more preferably a halogen atom or an alkyl group having 1 to 4 carbon atoms. Is most preferred.

Here, the aliphatic group means an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

The 5- or 6-membered ring formed by Z ¹¹ and Z ¹² is preferably an aromatic ring or a heteroaromatic ring, for example, a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, Pyrazole ring,
There are 1,2,3-triazole ring, 1,2,4-triazole ring, selenazole ring, oxadiazole ring, thiadiazole ring, benzene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Among these, Z ¹¹ is preferably a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a benzene ring and a pyridine ring, and more preferably a thiazole ring, a pyrrole ring, a benzene ring and a pyridine ring, A benzene ring is most preferred. Imidazole ring as Z ^12, a thiazole ring, an oxazole ring, a pyrrole ring,
Pyrazole ring, 1,2,3-triazole ring, 1,2,
A 4-triazole ring, a pyridine ring and a pyrimidine ring are preferred, an imidazole ring, a thiazole ring, a pyrrole ring, a pyrazole ring, a pyridine ring and a pyrimidine ring are more preferred, and a pyrazole ring and a pyridine ring are more preferred. Desirable Z ¹¹ and Z ¹² each have 3 to 4 carbon atoms.
0, more preferably 3 to 30, and particularly preferably 3 to 20.

Ln¹Represents a divalent group. Divalent group
For example, -C (R¹³¹) (R¹³²)-, -N (R¹³³)
-, -O-, -P (R¹³⁴)-Or -S-
You. Where R¹³¹And R¹³²Are independently hydrogen sources
Child, halogen atom, aliphatic group, aryl group, hetero ring
Group, cyano, -OR¹⁴¹, -SR¹⁴², -CO_TwoR¹⁴³, −
OCOR¹⁴⁴, -NR¹⁴⁵R¹⁴⁶, -CONR¹⁴⁷R¹⁴⁸,
-SO_TwoR¹⁴⁹, -SO_TwoNR^{Fifteen 0}R¹⁵¹, -NR¹⁵²CON
R¹⁵³R¹⁵⁴, -NR¹⁵⁵CO_TwoR¹⁵⁶, -COR¹⁵⁷, -N
R¹⁵⁸COR¹⁵⁹Or -NR¹⁶⁰SO_TwoR¹⁶¹Represents
R¹⁴¹, R¹⁴², R¹⁴³, R¹⁴⁴, R¹⁴⁵, R¹⁴⁶, R¹⁴⁷,
R¹⁴⁸, R¹⁴⁹, R¹⁵⁰, R¹⁵¹, R¹⁵², R¹⁵³, R ¹⁵⁴,
R¹⁵⁵, R¹⁵⁶, R¹⁵⁷, R¹⁵⁸, R¹⁵⁹, R¹⁶⁰And R
¹⁶¹Are each independently a hydrogen atom, an aliphatic group or an ant.
A group. R¹³³Represents an aliphatic group, an aryl group or
Represents a telocyclic group;¹³⁴Is an aliphatic group, aryl
Group, heterocyclic group and -OR¹⁷¹And R¹⁷¹Is water
A hydrogen atom, an aliphatic group or an aryl group.

Ln ¹ is preferably -C (R ¹³¹ ) (R
¹³² )-, -O- or -S-, more preferably -C ( ^R131 ) ( ^R132 )-, wherein ^R131 and ^R132 are a hydrogen atom, an aliphatic group or an aryl group; Preferably -C (R ¹³¹ ) (R ¹³² ) ^-represents R ¹³¹ and R
¹³² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The number of carbon atoms of Ln ¹ is preferably 0 to 20, more preferably 0 to 15, and particularly preferably 0 to 10.

Y ¹ represents a nitrogen atom or a carbon atom.
When Y ¹ is a nitrogen atom, b ¹ represents a single bond, and when Y ¹ is a carbon atom, b ¹ represents a double bond.

In the general formula (7), Z^{twenty one}And Z^{twenty two}Is 5
Non-metallic atomic groups necessary to form a six-membered or six-membered ring
And the ring may have a substituent, and
It may form a condensed ring with another ring. Examples of substituents include
Halogen atom, aliphatic group, aryl group, heterocyclic group,
Ano, nitro, -OR²⁰¹, -SR²⁰², -CO_TwoR²⁰³,
-OCOR²⁰⁴, -NR²⁰⁵R²⁰⁶, -CONR
²⁰⁷R²⁰⁸, -SO_TwoR²⁰⁹, -SO_TwoNR²¹⁰R²¹¹, -N
R²¹²CONR²¹³R²¹⁴, -NR²¹⁵CO_TwoR²¹⁶, -CO
R²¹⁷, -NR²¹⁸COR²¹⁹Or -NR²²⁰SO_TwoR²²¹
Is mentioned. Where R ²⁰¹, R²⁰², R²⁰³, R²⁰⁴, R
²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹, R²¹⁰, R^{twenty one 1}, R
²¹², R²¹³, R²¹⁴, R²¹⁵, R²¹⁶, R²¹⁷, R²¹⁸, R
²¹⁹, R²²⁰And R ²²¹Is independently a hydrogen atom,
It is an aliphatic group or an aryl group.

Preferred substituents for Z ²¹ and Z ²² are exactly the same as those for Z ¹¹ and Z ¹² .

The 5-membered and 6-membered rings formed by Z ²¹ include a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring,
There are a 2,3-triazole ring, 1,2,4-triazole ring, selenazole ring, oxadiazole ring, thiadiazole ring, benzene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Of these, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a benzene ring and a pyridine ring are preferred, a thiazole ring, a pyrrole ring, a benzene ring and a pyridine ring are more preferred, and a benzene ring is most preferred. . Z ²² is a pyrazole ring, 1, 2, 3
A triazole ring, a 1,2,4-triazole ring and a pyridazine ring, with a pyrazole ring being most preferred. Desirable Z ¹¹ and Z ¹² each have 3 to 40 carbon atoms,
More preferably, it is 3 to 30, particularly preferably 3 to 30.
20.

Y ² represents a nitrogen atom or a carbon atom.
When Y ² is a nitrogen atom, b ² represents a single bond, and when Y ² is a carbon atom, b ² represents a double bond.

In the general formula (8), X ²⁰¹ , X
²⁰² , X ²⁰³ and X ^{204 each} represent a nitrogen atom or CR, form a nitrogen-containing heteroaryl 6-membered ring together with -C = N-, and at least one of X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ Represents a nitrogen atom. The nitrogen-containing heteroaryl 6-membered ring formed by X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ together with -C = N- may form a condensed ring. R represents a hydrogen atom or a substituent, and the substituent has the same meaning as described for R ¹ and R ² . Preferred are pyrazine, pyrimidine, pyridazine, triazine, quinoxaline, quinazoline, phthalazine, cinnoline, purine, pteridine and the like, and more preferred are pyrazine, pyrimidine, pyridazine, quinoxaline, quinazoline, phthalazine and cinnoline. Z ^{20 1} represents an atomic group necessary for forming an aryl ring or heteroaryl ring. Aryl ring Z ²⁰¹ is formed, preferably having 6 to 30 carbon atoms, more preferably having a carbon number of 6 to 2
0, particularly preferably 6 to 12 carbon atoms, such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and the like, and may further form a condensed ring with a carbocycle or a heterocycle. The heteroaryl ring represented by Z ²⁰¹ preferably represents a heteroaryl ring composed of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, more preferably represents a 5- or 6-membered heteroaryl ring, and further forms a condensed ring. And preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 1 carbon atoms.
0, for example, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, quinoxaline, phthalazine, quinazoline, naphthodine, cinnoline, perimidine, phenanthroline, pyrrole, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiadiazole, benzimidazole, Examples include benzoxazole, benzothiazole, phenanthridine, thienyl group, furyl group and the like. The ring formed by Z ²⁰¹ is preferably an aryl ring.

In the general formula (9), Z ²⁰¹ has the same meaning as in the general formula (8), and Z ³⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring condensed with a pyridine ring. And the heteroaryl ring is the same as the aryl ring and the heteroaryl ring formed by Z ^{201 in the} general formula (8). The ring formed by Z ³⁰¹ is preferably an aryl ring.

In the general formula (10), Z ²⁰¹ has the same meaning as in the general formula (8), and Z ⁴⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring condensed with a pyridine ring. And the heteroaryl ring is the same as the aryl ring and the heteroaryl ring formed by Z ^{201 in the} general formula (8). Ring Z ⁴⁰¹ forms an aryl ring.

Further preferred forms of the compounds of the invention are
Compounds represented by the general formulas (11) to (20). Compounds represented by formulas (11) and (12) and compounds represented by formulas (14) and (20) are particularly preferred.

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The general formula (11) will be described. R ¹¹ ,
R ¹² represents a substituent, and examples of the substituent include those described above for R ¹ .

R ¹¹ and R ¹² are preferably an alkyl group or an aryl group, more preferably an alkyl group.

Q ¹¹ represents an integer of 0 to 2, preferably 0, 1 and more preferably 0. q ¹² represents an integer of 0 to 4,
0 and 1 are preferable, and 0 is more preferable. q ¹¹ and q ¹² are 2
In the above case, a plurality of R ¹¹ and R ¹² may be the same or different from each other, or may be linked to form a condensed ring.

L ¹ represents a ligand. Examples of the ligand include a ligand necessary for forming the above-mentioned orthometallated iridium complex, and the ligands described in other ligands. L ¹ is preferably a ligand necessary for forming an orthometallated iridium complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, and more preferably, an orthometalated iridium complex. Necessary ligand, bipyridyl ligand.

N ¹ represents 0 to 5, preferably 0. m ¹ represents ¹ , 2, 3 and is preferably 3. As the combination of the numbers n ¹ and m ¹ , a combination of numbers in which the metal complex represented by the general formula (4) becomes a neutral complex is preferable.

The general formula (12) will be described. R ²¹ ,
n ² , m ² , and L ² have the same meanings as R ¹¹ , n ¹ , m ¹ , and L ¹ , respectively. q ²¹ represents 0 to 8, 0 is preferable. When q ²¹ is 2 or more, a plurality of R ²¹ may be the same or different from each other, and may be linked to form a condensed ring.

The general formula (13) will be described. R ³¹ ,
R ³² , q ³¹ , q ³² , n ³ , m ³ , and L ³ are R ¹ ,
It is synonymous with R ² , q ¹ , q ² , n ¹ , m ¹ , and L ¹ .

The general formula (14) will be described.
R ³⁰¹ and R ³⁰² each represent a substituent, and the substituent has the same meaning as that described for Z ¹¹ and Z ¹² . q ³⁰¹ and q ³⁰² are 0
Represents an integer of ４4, and when q ³⁰¹ and q ³⁰² are 2 to 4, R
³⁰¹ and R ³⁰² may be the same or different. Preferred q
³⁰¹ and q ³⁰² are 0 or 1-2, and more preferably 0.
~ 1. m ¹⁰¹ , L ¹⁰¹ , and n ¹⁰¹ are each the aforementioned m ¹ ,
It is synonymous with L ¹ and n ¹ .

The general formula (15) will be described. L ¹⁰²
Has the same meaning as the L ^1, n ¹⁰² represents an integer of 0 to 5, 1 to 5 is preferred. m ¹⁰² represents an integer of 1 to 6, preferably 1 or 2. The number of combinations of n ¹⁰² and m ¹⁰² is a combination of several metal complex represented by the general formula (15) becomes neutral complexes are preferred.

The general formula (16) will be described.
L ^103, n ^103, m ¹⁰³ has the same meaning as ^{L 1, n 10 2, m} 102 respectively.

The general formula (17) will be described. R ³⁰³
Represents a substituent, and the substituent has the same meaning as that described for Z ²¹ . Z ²³ , q ³⁰³ , L ¹⁰⁴ , n ¹⁰⁴ , and m ¹⁰⁴ have the same meanings as Z ²² , q ³⁰¹ , L ¹ , n ¹⁰¹ , and m ¹⁰¹ , respectively.

The general formula (18) will be described. In the general formula (18), the ring formed by X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ together with —C ＝ N— is the same as that described in the general formula (8), and the preferable range is also the same. . Z
²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring, and is the same as that described in the formula (8), and the preferable range is also the same. n ²⁰¹ , m ²⁰¹ , L ²⁰¹
Is synonymous with n ¹ , m ¹ , and L ¹ , respectively.

In the general formula (19), Z ²⁰¹ and Z ³⁰¹ are the same as those described in the general formula (9), and the preferred range is also the same. n ²⁰² , m ²⁰² , and L ²⁰² have the same meanings as n ¹ , m ¹ , and L ¹ , respectively.

In the general formula (20), Z ²⁰¹ and Z ⁴⁰¹ are the same as those described in the general formula (10), and the preferred range is also the same. n ²⁰³ , m ²⁰³ , and L ²⁰³ have the same meanings as n ¹ , m ¹ , and L ¹ , respectively.

The compound of the present invention may be a so-called low molecular weight compound having one repeating unit of the general formula (1) or a so-called oligomer compound having a plurality of repeating units of the general formula (1) or the like. , A polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1
000-5,000,000, more preferably 2000-1
000000, more preferably 3000-10000
0. ). The compound of the present invention is preferably a low molecular compound.

Next, examples of the compound used in the present invention are shown, but the present invention is not limited thereto.

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The compound of the present invention can be prepared by the method described in Inorg. Chem. 1991, 30.
No., p.1685, 1988, 27, p.3464, 1994, 33,545.
, Inorg.Chem.Acta 1991, 181, 245, J. Organ.
omet.Chem. 1987, 335, 293., J. Am. Chem. Soc. 19
It can be synthesized by various known methods, such as 1985, No. 107, p. 1431.

Some of the synthesis examples of the compound of the present invention are shown below. As shown below, iridium hexahalide (II
It can also be synthesized using I) a compound and an iridium (IV) hexahalide compound as a starting material.

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(Synthesis Example 1) Synthesis of Exemplified Compound (1-25) 5.23 g of K ₃ IrCl ₆ , 16.9 g of 2-benzylpyridine and 50 ml of glycerol were placed in a _three- necked flask and placed under an argon atmosphere. The mixture was stirred for 1 hour while heating the internal temperature to 200 ° C. Thereafter, the mixture was cooled until the internal temperature reached 40 ° C., and 150 ml of methanol was added. After stirring for 1 hour as it was, the crystals obtained by suction filtration were purified by silica gel column chromatography to obtain 4.34 g of the desired exemplified compound (1-25) (yield 77%).

(Synthesis Example 2) Synthesis of Exemplified Compound (1-24) 5.64 of Exemplified Compound (1-25) in a three-necked flask.
g, chloroform 560 ml, acetylacetone 10.
Then, 20.1 ml of a 28% methanol solution of sodium methylate was added thereto while stirring at room temperature.
Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then 40 ml of saturated saline and 400 ml of water were added for extraction. The obtained chloroform layer was washed with saturated saline (300 ml).
After washing four times with a mixed solution of water and 30 ml of water, the solution was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to give the desired exemplary compound (1-24)
Was obtained (yield 89%).

(Synthesis Example 3) Synthesis of Exemplified Compound (1-26) 6.28 Exemplified Compound (1-24) was placed in a three-necked flask.
g, 15.5 g of 2-phenylpyridine and 63 ml of glycerol, and the internal temperature was 170 ° C. under an argon atmosphere.
And stirred for 15 minutes. After this the internal temperature is 40 ° C
, And extracted by adding 500 ml of chloroform, 40 ml of saturated saline and 400 ml of water. The obtained chloroform layer was washed with 40 ml of saturated saline and 400 ml of water.
Was washed four times with a mixture of the above, and dried over anhydrous sodium sulfate. The residue was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 5.60 g of the desired exemplary compound (1-26).
Was obtained (yield 82%).

Synthesis Example 4 Synthesis of Exemplified Compound (1-29) 5.64 g of Exemplified Compound (1-25) was placed in a three-necked flask.
560 ml of chloroform was put therein, and carbon monoxide was blown into this for 10 minutes while stirring in a water bath. After that, stirring was continued for 1 hour, and then 40 ml of saturated saline and 400 ml of water.
Was added and extracted. The obtained chloroform layer was washed four times with a mixed solution of 300 ml of saturated saline and 30 ml of water, dried over anhydrous sodium sulfate, and concentrated with a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to obtain 4.38 g of the desired exemplified compound (1-29) (yield 74%).

Synthesis Example 5 Synthesis of Exemplified Compounds (1-65) and (1-66)

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3-chloro-6-phenylpyridazine was prepared by dissolving 1.35 g of K ₃ IrCl ₆ in 25 ml of water.
01 g and 100 ml of glycerin, and
The mixture was heated and stirred for hours. After completion of the reaction, the mixture was left to cool, water was added,
The precipitated dark brown solid was collected by filtration and dried. Next, 2.5 g of acetylacetone and 4.8 g of a 28% methanol solution of sodium methoxide were added to a solution of the obtained solid in 1 L of chloroform, and the mixture was reacted under heating and reflux for 2 hours. After completion of the reaction, the mixture was poured into 500 ml of water and extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated, and the obtained solid was developed by silica gel column chromatography. The orange fraction eluted first is concentrated, recrystallized from chloroform-ethanol, and dried.
66 mg of the desired Exemplified Compound 1-65 was obtained. When the solution fluorescence spectrum of this compound was measured, the fluorescence λmax
= 578 nm (CHCl ₃ ). Further, the red-orange fraction eluted next was concentrated, recrystallized from chloroform-ethanol, and dried to obtain 294 mg of the desired Exemplified Compound 1-66. When the solution fluorescence spectrum of this compound was measured, the fluorescence λmax = 625 nm (CHC
l ₃ ).

Next, a light emitting device containing the compound of the present invention will be described. The light emitting device of the present invention is not particularly limited as long as it is a device using the compound of the present invention, such as a system, a driving method, and a use form. The thing used as is preferred. Organic EL as a typical light emitting element
(Electroluminescence) elements.

The method for forming the organic layer of the light emitting device containing the compound of the present invention is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination,
A method such as a coating method, an ink-jet method, or a printing method is used, and resistance heating evaporation and a coating method are preferable in terms of characteristics and production, and a coating method is more preferable in terms of avoiding thermal decomposition during the evaporation.

The light emitting device of the present invention is a device in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer is formed between a pair of anode and cathode electrodes. , An electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like. A metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof is used. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, one having a layer formed on a soda lime glass, an alkali-free glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. The anode can be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment and the like are effective.

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer, etc., and provides the adhesion between the negative electrode such as the electron injecting layer, the electron transporting layer, the light emitting layer, the ionization potential, and the like. It is selected in consideration of stability and the like. As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples thereof include an alkali metal (for example, L
i, Na, K, etc.) and their fluorides, alkaline earth metals (eg, Mg, Ca, etc.) and their fluorides, gold, silver,
Lead, aluminum, a sodium-potassium alloy or a mixed metal thereof, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium and the like, preferably a work function Is a material of 4 eV or less, more preferably aluminum, lithium-aluminum alloy or a mixed metal thereof, magnesium-
It is a silver alloy or a mixed metal thereof. The cathode can have not only a single-layer structure of the compound and the mixture, but also a stacked structure including the compound and the mixture. The thickness of the cathode can be appropriately selected depending on the material, but is usually from 10 nm to
It is preferably in the range of 5 μm, more preferably 50 n
m to 1 μm, more preferably 100 nm to 1 μm
It is. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer is capable of injecting holes from an anode, a hole injection layer, or a hole transport layer and applying electrons from a cathode, an electron injection layer, or an electron transport layer when an electric field is applied. Any function can be used as long as it can form a layer having a function of transferring injected charges, a function of providing a field of recombination of holes and electrons and emitting light, and is a singlet exciton or triplet. It may emit light from any of the term excitons. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives , Metal complexes and rare earth complexes of pyrrolidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives Polymer compounds such as polythiophene, polyphenylene, and polyphenylenevinylene, such as various metal complexes,
Organic silane derivatives, compounds of the present invention, and the like are included. Although the thickness of the light emitting layer is not particularly limited, it is usually 1n.
m to 5 μm, more preferably 5 to 5 μm.
nm to 1 μm, more preferably 10 nm to 500
nm. The method for forming the light emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), ink jet, and LB. , A printing method, and the like, and preferably a resistance heating evaporation and a coating method.

The material of the hole injection layer and the hole transport layer has one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Should be fine. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic silane derivatives, carbon films, and the compounds of the present invention. The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually 1
It is preferably in the range of nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 50 μm.
0 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Etc.), an inkjet method, and a printing method. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, or a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic anhydrides such as fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene perylene, and phthalocyanine derivatives And various metal complexes typified by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as ligands, and organic silane derivatives. The thickness of the electron injecting layer and the electron transporting layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 1 μm.
nm to 500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injecting layer and the electron transporting layer include a vacuum evaporation method, an LB method, a method in which the electron injecting and transporting agent is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, etc.), An ink jet method, a printing method, or the like is used.
In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing a substance that promotes element deterioration such as moisture and oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ , Al ₂ O ₃ , G
eO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O 3, T
metal oxides such as iO ₂ , MgF ₂ , LiF, AlF ₃ , C
aF ₂ metal fluorides such as, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, poly-dichloro-difluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, At least one with tetrafluoroethylene
A copolymer obtained by copolymerizing a monomer mixture containing a kind of comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0.1% The following moisture-proof substances are listed. There is no particular limitation on the method of forming the protective layer, for example, a vacuum evaporation method,
Sputtering method, reactive sputtering method, MBE
(Molecular beam epitaxy) method, cluster ion beam method,
An ion plating method, a plasma polymerization method (high-frequency excitation ion plating method), a plasma CVD method, a laser CVD method, a thermal CVD method, a gas source CVD method, a coating method, and a printing method can be applied.

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EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

Comparative Example 1 Poly (N-vinylcarbazole) 40 mg, PBD (2
-(4-biphenyl) -5- (4-t-butylphenyl)-
1,3,4-oxadiazole) 12 mg, compound A
1 mg was dissolved in 2.5 ml of dichloroethane and spin-coated on a washed substrate (1500 rpm, 20 seconds).
c). The thickness of the organic layer was 98 nm. A mask (a mask having a light-emitting area of 4 mm × 5 mm) patterned on the organic thin film was provided, and magnesium: silver = 10: 1 was co-deposited in a vapor deposition apparatus at 50 nm, and then silver was vapor-deposited at 50 nm. Toyo Technica Source Measure Unit 2400
Using a mold, apply a DC constant voltage to the EL element to emit light,
The luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength was measured using a spectrum analyzer PMA-1 manufactured by Hamamatsu Photonics.
1 was measured. As a result, λmax of light emission = 50
A green emission of 0 nm was obtained. The external quantum yield calculated at around 100 cd / m ² was 0.1%.
When left under nitrogen for one hour, many dark spots were visually observed on the light emitting surface.

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Example 1 A device was prepared in the same manner as in Comparative Example 1, except that (1-1) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 510n
A green light emission of m ² was obtained, and the external quantum yield at around 100 cd / m ² was 2.9%. When left under nitrogen for 1 hour, a small amount of dark spot was observed on the light emitting surface. Example 2 A device was produced in the same manner as in Comparative Example 1, except that (1-2) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 510n
m 2 green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 3 A device was produced in the same manner as in Comparative Example 1, except that (1-3) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 590n
m 2 orange light emission was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 4 An element was produced in the same manner as in Comparative Example 1, except that (1-4) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 510n
m 2 green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 5 A device was prepared in the same manner as in Comparative Example 1, except that (1-20) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 547
nm emission of green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 6 A device was prepared in the same manner as in Comparative Example 1, except that (1-24) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 530
nm emission of green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 7 A device was prepared in the same manner as in Comparative Example 1, except that (1-25) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 564
nm emission was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 8 A device was prepared in the same manner as in Comparative Example 1, except that (1-36) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 520
nm emission of green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 9 A device was prepared in the same manner as in Comparative Example 1, except that (1-41) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 513
A green emission of nm was obtained, and the external quantum efficiency at around 100 cd / m ² was 5.1%. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 10 An element was produced in the same manner as in Comparative Example 1, except that (1-42) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 535
nm emission of green light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 11 A device was prepared in the same manner as in Comparative Example 1, except that (1-44) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 532
nm emission of orange light was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 12 A device was produced in the same manner as in Comparative Example 1, except that (1-46) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 568
nm yellow emission was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 13 A device was prepared in the same manner as in Comparative Example 1, except that (1-65) was used in place of Compound A in Comparative Example 1. Λmax of light emission = 578
nm yellow-orange emission was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible. Example 14 An element was produced in the same manner as in Comparative Example 1, except that (1-66) was used instead of Compound A in Comparative Example 1. Λmax of light emission = 625
nm red-orange emission was obtained. It was left under nitrogen for 1 hour, but no dark spot was visible.

Example 15 A cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD
(N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine) was vapor-deposited to a thickness of 40 nm, and Compound B and the compound of the present invention (1-46) were further deposited thereon in the ratio of (10: 1). 24 nm was co-deposited, and compound C was further deposited thereon to a thickness of 24 nm.
Evaporated. A mask (a mask having a light-emitting area of 4 mm × 5 mm) patterned on the organic thin film was provided, and magnesium: silver = 10: 1 was co-evaporated in a vapor deposition apparatus at 250 nm, and then silver was vapor-deposited at 250 nm. As a result of applying a DC constant voltage to the EL element to emit light, λmax of light emission = 567n
m of yellow luminescence was obtained, and the external quantum efficiency was 13.6% (1
85 cd / m ² hour).

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Example 16 A cleaned ITO substrate was placed in a vapor deposition apparatus, and α-NPD
(N, N'-diphenyl-N, N'-di (α-naphthyl) -benzidine) was vapor-deposited to a thickness of 40 nm, and the compound of the present invention (1-42) was co-deposited thereon to a thickness of 20 nm. Was deposited to a thickness of 40 nm. A mask (a mask having a light emitting area of 4 mm × 5 mm) patterned on the organic thin film is provided, and magnesium: silver = 1 in a vapor deposition apparatus.
After 250 nm of 0: 1 was co-evaporated, 250 nm of silver was evaporated. As a result of applying a DC constant voltage to the EL element to emit light,
A yellow-green emission of λmax = 535 nm was obtained, and the external quantum efficiency was 3.1% (at 120 cd / m ² ).

Example 17 40 mg of poly (N-vinylcarbazole) and PBD (2
-(4-biphenyl) -5- (4-t-butylphenyl)-
12 mg of 1,3,4-oxadiazole) and 1 mg of the present compound (1-49) were dissolved in 2.5 ml of dichloroethane, and spin-coated on a washed substrate (1500).
rpm, 20 sec). The thickness of the organic layer was 98 nm. Put it in a vapor deposition device and put compound C on the organic film.
0 nm was deposited. A mask (a mask having a light emitting area of 4 mm × 5 mm) patterned on the organic thin film is installed,
After 5 nm of lithium fluoride was evaporated in the evaporation apparatus, 500 nm of aluminum was evaporated. As a result of applying a DC constant voltage to the EL element to emit light, λmax of light emission = 580 n
m of orange emission was obtained, and the external quantum efficiency was 4.2% (10%).
00 cd / m ² hour).

Example 18 Baytron P (PEDOT-PSS solution (polyethylene dioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated (1000 rpm, 30 sec) on a washed substrate, and heated at 150 ° C. for 1 hour. Vacuum dried for 0.5 hours. The thickness of the organic layer was 70 nm. On top of this, poly (N-vinylcarbazole) 40
mg, PBD (2- (4-biphenyl) -5- (4-t-
(Butylphenyl) -1,3,4-oxadiazole) 1
2 mg and 1 mg of the compound of the present invention (1-42) were dissolved in 2.5 ml of dichloroethane, and spin-coated on a washed substrate (1500 rpm, 20 sec). The thickness of the total organic layer was 170 nm. A mask patterned on an organic thin film (a mask with a light emitting area of 4 mm x 5 mm)
Was installed, and magnesium: silver = 10: 1 was co-evaporated at 250 nm in a vapor deposition apparatus, and then 250 nm of silver was vapor-deposited. As a result of applying a DC constant voltage to the EL element to emit light,
Yellow-green light emission of max = 540 nm was obtained, and the external quantum efficiency was 6.2% (at 2000 cd / m ² ). Similarly,
When the compound-containing EL device of the present invention was prepared and evaluated,
It was confirmed that high-efficiency EL devices having various luminescent colors could be manufactured, and the durability was excellent. In addition, a vapor-doped device using the compound of the present invention can emit light with high efficiency, and a device having a single-layer light-emitting material can emit light with high efficiency.

[0122]

Industrial Applicability The compound of the present invention can be used as a material for an organic EL, and has high efficiency having various luminescent colors.
A highly durable EL element can be manufactured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 213/28 C07D 213/28 4C065 213/68 213/68 4H050 213/84 213/84 217/02 217 / 02 221/10 221/10 231/12 231/12 C 237/12 237/12 241/16 241/16 263/56 263/56 409/04 409/04 471/04 112 471/04 112T H05B 33/14 H05B 33/14 B // C07F 15/00 C07F 15/00 E (72) Inventor Kazumi Arai 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 3K007 AB03 CA01 CB01 DA02 DB03 EB00 FA01 4C034 AA09 CE01 4C055 AA15 BA02 BA05 BA06 BA08 BA42 BB01 BB02 CA01 DA01 DA25 4C056 AA01 AB01 AC02 AD03 AE03 CA03 CC01 CD01 4C063 AA01 BB01 CC92 DD12 EE10 4C065 AA04 AA19 BB09 CC09 DD02 EE02 H0101WB01A01 BB02

Claims (14)

[Claims] 1. A light emitting device material comprising a compound having a partial structure represented by the general formula (1) or a tautomer thereof. Embedded image 2. A light emitting device material comprising a compound having a partial structure represented by the general formula (2) or a tautomer thereof. Embedded image 3. A light emitting device material comprising a compound having a partial structure represented by the general formula (3) or a tautomer thereof. Embedded image In the formula, R ¹ and R ² each represent a substituent. q ¹ and q ² are 0
Represents an integer of 4 to 4, and q ¹ + q ² is 1 or more. 4. A compound having a partial structure represented by the general formula (4) or a tautomer thereof. Embedded image In the formula, Z ¹¹ and Z ¹² each represent a nonmetallic atomic group necessary for forming a 5- or 6-membered ring together with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. Alternatively, a condensed ring may be formed with another ring. Ln ¹ represents a divalent group. Y ¹ represents a nitrogen atom or a carbon atom, and b ¹ represents a single bond or a double bond. 5. A luminescent material comprising the compound according to claim 4. 6. A luminescent material comprising a compound having a partial structure represented by the general formula (5). Embedded image 7. A luminescent material comprising a compound having a partial structure represented by the general formula (6). Embedded image 8. A luminescent material comprising a compound having a partial structure represented by the general formula (7) or a tautomer thereof. Embedded image In the formula, Z ²¹ and Z ²² each represent a non-metallic atomic group necessary for forming a 5- or 6-membered ring together with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. It may form a condensed ring with another ring. Y ² represents a nitrogen atom or a carbon atom, and b ² represents a single bond or a double bond. 9. A luminescent material comprising a compound having a partial structure represented by the general formula (8) or a tautomer thereof. Embedded image In the formula, X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ represent a nitrogen atom or C—R, and form a nitrogen-containing heteroaryl 6-membered ring together with —C ＝ N—, X ²⁰¹ , X ²⁰² , X ²⁰³ And X
^At least one of ²⁰⁴ represents a nitrogen atom. R represents a hydrogen atom or a substituent. Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring. 10. A luminescent material comprising a compound having a partial structure represented by the general formula (9) or a tautomer thereof. Embedded image In the formula, Z ²⁰¹ and Z ³⁰¹ each represent an atomic group forming an aryl ring or a heteroaryl ring. 11. A luminescent material comprising a compound having a partial structure represented by the general formula (10) or a tautomer thereof. Embedded image In the formula, Z ²⁰¹ and Z ⁴⁰¹ represent an atomic group forming an aryl ring or a heteroaryl ring. 12. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one of the light-emitting elements has at least one layer.
An organic light-emitting device containing the light-emitting material according to 1. 13. A light-emitting element comprising a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer between a pair of electrodes, wherein the light-emitting material is a single layer of the light-emitting material according to claim 1, 2, 3, 5 or 11. An organic light-emitting device comprising at least one layer of: 14. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one layer has an ortho-metallated iridium complex, and the ortho-metallated iridium complex has at least one layer. A light-emitting element characterized in that a layer containing a film is formed by a coating process.