JP5124942B2 - Metal complexes and devices - Google Patents

Description

  The present invention relates to a metal complex and a device.

  As a light emitting material used for a light emitting layer of an electroluminescence (EL) light emitting element, a metal complex that emits light from a triplet excited state is known.

  As a metal complex that exhibits light emission from a triplet excited state, a metal complex having a bidentate ligand as a ligand is known. (Non-Patent Document 1)

In order to improve the properties of the metal complex having the bidentate ligand, metal complexes having a tridentate ligand and a monodentate ligand have been studied. (Non-Patent Documents 2 and 3)

APPLIED PHYSICS LETTERS, 75, 1, 4, (1999) Organometallics 1998, 17, 3505-3511 Zeitschrift fuer Naturforschung (1964), 19b (8), 767-8.

However, the known metal complexes having a tridentate ligand and a monodentate ligand have not been sufficient in their light emission performance.

  An object of the present invention is to provide a metal complex having a tridentate ligand and a monodentate ligand and capable of exhibiting sufficient light emission performance.

That is, the present invention includes a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au, and a lanthanoid, a monodentate ligand, one or more aromatic rings, and the aromatic ring structure. The present invention provides a metal complex having a tridentate ligand containing three coordinating atoms, and which emits light in the visible region at 10 ° C. or higher.

The metal complex of the present invention has a monodentate ligand and a tridentate ligand, and can exhibit sufficient light emission performance.

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The metal of the metal complex of the present invention is a metal selected from the transition metals of the fourth and fifth periods and W, Os, Ir, Au, and lanthanoid, and specific examples thereof include Sc, Ti, Cr, Mn, Fe , Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Os, Ir, Au, La, Ce, Pr, Nd, Pm, Sm Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu are examples. From the viewpoint of obtaining high efficiency, Ru, Rh, W, Os, Ir, Au, Eu, and Tb are preferable. Further, W, Os, Ir and Au are preferable, W and Au are more preferable, and Au is most preferable.

The monodentate ligand of the metal complex of the present invention includes a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, acyl group, amide group, acid imide group, amino group, silyl group Group, carboxyl group, heterocyclic ligand, carbonyl ligand, alkene ligand, alkyne ligand, amine ligand, imine ligand, isonitrile ligand, phosphine ligand, phosphine oxide coordination Examples thereof include a child, a phosphite ligand, an ether ligand, a sulfone ligand, a sulfoxide ligand, or a sulfide ligand. Any ligand may be substituted by a halogen atom such as fluorine or chlorine.

The alkyl group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc., and pentyl group Hexyl group, octyl group, 2-ethylhexyl group, decyl group and 3,7-dimethyloctyl group are preferred.

The alkoxy group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorohexyl group Fluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, and pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, 3,7-dimethyloctyloxy group preferable.

The alkylthio group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2- Examples include ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like. Pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, 3 , 7-dimethyloctylthio group is preferred.

The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms, and the same shall apply hereinafter), C _{1 to} C ₁₂ alkylphenyl. Groups, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, etc., and C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ Alkylphenyl groups are preferred. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

As an aryloxy group, carbon number is about 6-60 normally, Preferably it is 7-48. Specifically, a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group are exemplified, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group, Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

As an arylthio group, carbon number is about 6-60 normally, Preferably it is C7-48. Specifically, a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxy phenylthio group, C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specifically, formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoro Examples include an acetamide group and a dipentafluorobenzamide group.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples include the following groups.

The heterocyclic ligand may be zero-valent or monovalent, and examples of the zero-valent ligand include 2,2′-bipyridyl, 1,10-phenanthroline, 2- (4-thiophen-2-yl) pyridine, Examples include 2- (benzothiophen-2-yl) pyridine and the like, and monovalent ones include, for example, phenylpyridine, 2- (paraphenylphenyl) pyridine, 7-bromobenzo [h] quinoline, 2- (4-phenyl) Examples include thiophen-2-yl) pyridine, 2-phenylbenzoxazole, 2- (paraphenylphenyl) benzoxazole, 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole and the like.
Carbonyl ligands include ketones such as carbon monoxide, acetone and benzophenone, diketones such as acetylacetone and acenaphthoquinone, acetonate ligands such as acetylacetonate, dibenzomethylate, and tenoyltrifluoroacetonate. Illustrated.
The alkene ligand is not particularly limited, and examples thereof include ethylene, propylene, butene, hexene, and decene.
Although it does not specifically limit as an alkyne ligand, For example, acetylene, phenyl acetylene, diphenyl acetylene, etc. are mentioned.
Although it does not specifically limit as an amine ligand, For example, a triethylamine, a tributylamine, etc. are mentioned.
The imine ligand is not particularly limited, and examples thereof include benzophenone imine and methyl ethyl ketone imine.
The isonitrile ligand is not particularly limited, and examples thereof include t-butyl isonitrile and phenyl isonitrile.
The phosphine ligand is not particularly limited, and examples thereof include triphenylphosphine, tolylphosphine, tricyclohexylphosphine, and tributylphosphine.
Although it does not specifically limit as a phosphine oxide ligand, For example, a tributyl phosphine oxide or a triphenyl phosphine oxide etc. are mentioned.
Although it does not specifically limit as a phosphite ligand, For example, a triphenyl phosphite, a tolyl phosphite, a tributyl phosphite, a triethyl phosphite etc. are mentioned.
The ether ligand is not particularly limited, and examples thereof include dimethyl ether, diethyl ether, and tetrahydrofuran.
The sulfone ligand is not particularly limited, and examples thereof include dimethyl sulfone and dibutyl sulfone.
The sulfoxide ligand is not particularly limited, and examples thereof include dimethyl sulfoxide and dibutyl sulfoxide.
The sulfide ligand is not particularly limited, and examples thereof include ethyl sulfide and butyl sulfide.

The monodentate ligand preferably has an aromatic ring (a monodentate ligand having an aromatic ring), and more preferably includes a coordination atom in the aromatic ring structure (in the aromatic ring). More preferably, the coordination atom in the aromatic ring is carbon or nitrogen, or the aromatic ring is a condensed ring.

From the viewpoint of luminous efficiency, the monodentate ligand in which the coordination atom in the aromatic ring is carbon or nitrogen is preferably a structure represented by the following formula (S-1).

〔上記式（Ｓ−１）中、＊は金属に配位している原子を表し、Ｒはそれぞれ独立に水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。〕

[In the above formula (S-1), * represents an atom coordinated to a metal, and R is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, Arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, An acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group is shown. ]

Here, the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, acyl group, amide group, and acid imide group represent the same groups as described above.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl-C ₁ -C ₁₂ alkoxy groups such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenyloctyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ ~ such as C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferred.

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

The arylalkenyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The substituted amino group refers to an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, aryl group, arylalkyl group or The monovalent heterocyclic group may have a substituent. Carbon number is about 1-60 normally without including carbon number of this substituent, Preferably it is C2-48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

The substituted silyl group means a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 1 to 60 carbon atoms. Yes, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The imine residue is an imine compound (refers to an organic compound having —N═C— in the molecule. Examples thereof include aldimine, ketimine, and a hydrogen atom on these N substituted with an alkyl group or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

The substituted carboxyl group usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. A carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, which is a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an i-propoxycarbonyl group, a butoxycarbonyl group, an i-butoxy Carbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl Group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl , Perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, pyridyloxy carbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

From the viewpoint of luminous efficiency, the monodentate ligand which is a condensed ring is preferably a structure represented by the following formula (S-2).

〔上記式（Ｓ−２）中、＊は金属に配位している原子を表し、Ｒは前記と同様の基を表す。〕

[In the formula (S-2), * represents an atom coordinated to a metal, and R represents the same group as described above. ]

From the viewpoint of synthesis, in the formulas (S-1) and (S-2), R is preferably a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

In particular, when the tridentate ligand represented by the following formulas (1) to (3) does not contain a condensed ring, the monodentate ligand preferably has a condensed ring.

Next, the tridentate ligand will be described. The metal complex of the present invention has a tridentate ligand containing one or more aromatic rings and three coordinating atoms in the ring structure.
When this tridentate ligand contains one aromatic ring, it contains three coordinating atoms within the ring structure of this aromatic ring, and when it contains two aromatic rings, one ring per ring It contains a coordination atom and the other ring contains two coordination atoms. When the tridentate ligand contains three aromatic rings, for example, each ring contains one coordinating atom. At this time, the number of aromatic rings contained in the tridentate ligand does not include the number of aromatic rings contained in the substituent.

The aromatic ring contained in the tridentate ligand of the metal complex of the present invention may have a substituent,
Examples of the substituent include a halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid Imido group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group , Substituted carboxyl group, cyano group and the like. When a plurality of substituents are present on the aromatic ring of the tridentate ligand, they may be the same or different.

Here, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, The imine residue, substituted amino group, substituted silyl group, monovalent heterocyclic group, arylalkenyl group, arylalkynyl group and substituted carboxyl group are the same groups as described above.

The substituted silyloxy group refers to a silyloxy group substituted with 1, 2 or 3 groups selected from an alkoxy group, an aryloxy group, an arylalkoxy group or a monovalent heterocyclic oxy group, and usually has 1 to 60 carbon atoms. About 3 to 48 carbon atoms. The alkoxy group, aryloxy group, arylalkoxy group or monovalent heterocyclic oxy group may have a substituent.
Specifically, trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-i-propylsilyloxy group, dimethyl-i-propylsilyloxy group, diethyl-i-propylsilyloxy group, t- Butylsilyldimethylsilyl group, pentyldimethylsilyloxy group, hexyldimethylsilyloxy group, heptyldimethylsilyloxy group, octyldimethylsilyloxy group, 2-ethylhexyl-dimethylsilyloxy group, nonyldimethylsilyloxy group, decyldimethylsilyloxy group , 3,7-dimethyl octyl - dimethyl silyl group, lauryl dimethyl silyloxy group, a phenyl -C ₁ -C ₁₂ alkyl silyloxy groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl silyloxy groups, C _{1 to} C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl silyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl silyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl silyloxy group, phenyl -C ₁ -C ₁₂ alkyl Examples include dimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group, and dimethylphenylsilyloxy group. The

The substituted silylthio group means a silylthio group substituted with 1, 2 or 3 groups selected from an alkylthio group, an arylthio group, an arylalkylthio group or a monovalent heterocyclic thio group, and usually has about 1 to 60 carbon atoms. And preferably has 3 to 48 carbon atoms. The alkoxy group, arylthio group, arylalkylthio group or monovalent heterocyclic thio group may have a substituent.
Specifically, trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, tri-i-propylsilylthio group, dimethyl-i-propylsilylthio group, diethyl-i-propylsilylthio group, t-butyl Silyldimethylsilylthio group, pentyldimethylsilylthio group, hexyldimethylsilylthio group, heptyldimethylsilylthio group, octyldimethylsilylthio group, 2-ethylhexyl-dimethylsilylthio group, nonyldimethylsilylothio group, decyldimethylsilylthio group group, a 3,7-- dimethylsilylene group, a heteroarylthio group, lauryl dimethylsilylene thio group, a phenyl -C ₁ -C ₁₂ alkyl silyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ ₁₂ alkylsilylthio group, a 1-naphthyl -C ₁ -C ₁₂ alkylsilylthio group, a 2-naphthyl -C ₁ -C ₁₂ alkylsilylthio group, a phenyl -C ₁ -C ₁₂ alkyl dimethylsilylene group, a heteroarylthio group, triphenyl Siri Examples include a ruthio group, a tri-p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a t-butyldiphenylsilylothio group, and a dimethylphenylsilylthio group.

The substituted silylamino group means a silylamino group substituted with 1, 2 or 3 groups selected from an alkylamino group, an arylamino group, an arylalkylamino group or a monovalent heterocyclic amino group. It is about -60, Preferably it is C3-C48. The alkoxy group, arylamino group, arylalkylamino group or monovalent heterocyclic amino group may have a substituent.
Specifically, trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, tri-i-propylsilylamino group, dimethyl-i-propylsilylamino group, diethyl-i-propylsilylamino group, t- Butylsilyldimethylsilylamino group, pentyldimethylsilylamino group, hexyldimethylsilylamino group, heptyldimethylsilylamino group, octyldimethylsilylamino group, 2-ethylhexyl-dimethylsilylamino group, nonyldimethylsilylamino group, decyldimethylsilyl amino group, a 3,7-- dimethylsilyl group, lauryl dimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkyl silyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl amino group , ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ ~ C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- xylyl silyl group, tribenzylsilyl group, diphenylmethylsilyl amino group, t- butyl diphenyl silyl Oh amino group, a dimethylphenyl silyl amino group Etc. are exemplified.

As heteroaryloxy group, carbon number is about 6-60 normally, Preferably it is 7-48. Specifically, a thienyl group, C ₁ -C ₁₂ alkoxide Shichie alkenyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyloxy group, a pyridyloxy group, etc. isoquinolyloxy group and the like, C ₁ -C ₁₂ alkoxy a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkyl pyridyl group as such as methyl pyridyl group, ethyl pyridyloxy group, dimethylpyridyl group, propyl pyridyloxy group, 1,3,5-trimethyl-pyridyl group, methyl ethyl pyridyl group I-propylpyridyloxy group, butylpyridyloxy group, i-butylpyridyloxy group, t-butylpyridyloxy group, pentylpyridyloxy group, isoamylpyridyloxy group, hexylpyridyloxy group, heptylpyridyloxy group, octylpyridyloxy group Group, nonylpyridyloxy group, decylpyridyloxy group, dodecylpyridyloxy group and the like.

The heteroarylthio group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, pyridylthio, C ₁ -C ₁₂ alkoxy pyridylthio group, C ₁ -C ₁₂ alkylpyridylthio group, isoquinolylthio group and the like, C ₁ -C ₁₂ alkoxy pyridylthio group, C ₁ -C ₁₂ Alkylpyridylthio groups are preferred.

（１）

〔式中、Ｍは第４および第５周期の遷移金属並びにＷ，Ｏｓ、Ｉｒ、Ａｕおよびランタノイドから選ばれる金属を表し、Ａ環、Ｂ環およびＣ環はそれぞれ独立に芳香環を表し、各々の環構造内に存在しているＸ₁、Ｙ₁およびＺ₁は、それぞれ独立に金属Ｍへの配位原子を表わす。ｆおよびｇはそれぞれ独立に炭素数１〜６のアルキレン基、炭素数１〜６のアルケニレン基または炭素数１〜６のアルキニレン基を表し、該アルキレン基、該アルケニレン基および該アルキニレン基の炭素原子がそれぞれ酸素原子または硫黄原子で置換されていてもよい。ｍおよびｎはそれぞれ独立に０または１を表す。〕

（２）

〔式中、Ｍは第４および第５周期の遷移金属並びにＷ，Ｏｓ、Ｉｒ、Ａｕおよびランタノイドから選ばれる金属を表し、Ｄ環およびＥ環は、それぞれ独立に芳香環を表し、各々の環構造内に存在しているＸ₂、Ｙ₂およびＺ₂は、それぞれ独立に金属Ｍへの配位原子を表わし、ｈは炭素数１〜６のアルキレン基、炭素数１〜６のアルケニレン基または炭素数１〜６のアルキニレン基を表し、該アルキレン基、該アルケニレン基および該アルキニレン基の炭素原子がそれぞれ酸素原子または硫黄原子に置換されていてもよく、ｏは０または１を表す。〕

（３）
〔式中、Ｍは第４および第５周期の遷移金属並びにＷ，Ｏｓ、Ｉｒ、Ａｕおよびランタノイドから選ばれる金属を表し、Ｆ環は芳香環を表し、環構造内に存在するＸ₃，Ｙ₃およびＺ₃は、それぞれ独立に金属Ｍへの配位原子を表わす。〕 As the metal complex of the present invention, a metal complex having a structure represented by the following general formula (1), (2) or (3) and a monodentate ligand is preferable.

(1)

[Wherein, M represents a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au, and a lanthanoid, A ring, B ring and C ring each independently represent an aromatic ring, X ₁ , Y ₁ and Z ₁ existing in the ring structure of each independently represent a coordination atom to the metal M. f and g each independently represent an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms or an alkynylene group having 1 to 6 carbon atoms, and the carbon atoms of the alkylene group, the alkenylene group and the alkynylene group Each may be substituted with an oxygen atom or a sulfur atom. m and n each independently represents 0 or 1. ]

(2)

[Wherein, M represents a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au, and a lanthanoid, D ring and E ring each independently represent an aromatic ring, X ₂ , Y ₂ and Z ₂ present in the structure each independently represent a coordination atom to the metal M, and h represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, or Represents an alkynylene group having 1 to 6 carbon atoms, and the carbon atom of the alkylene group, the alkenylene group and the alkynylene group may be substituted with an oxygen atom or a sulfur atom, respectively, and o represents 0 or 1. ]

(3)
[Wherein M represents a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au, and a lanthanoid, the F ring represents an aromatic ring, and X ₃ , Y existing in the ring structure ₃ and Z ₃ each independently represent a coordination atom to the metal M. ]

  M in the above formula (1) is a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au and lanthanoid, and specific examples thereof include Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Os, Ir, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu are examples. From the viewpoint of obtaining high efficiency, Ru, Rh, W, Os, Ir, Au, Eu, and Tb are preferable. W, Os, Ir and Au are preferable, W and Au are more preferable, and Au is most preferable.

In the above formula (1), A ring, B ring and C ring each independently represent an aromatic ring.
Examples of the aromatic ring include an aromatic hydrocarbon ring and a heteroaromatic ring. The aromatic ring may be a single ring or a condensed ring.

Examples of the monocyclic aromatic hydrocarbon ring include benzene.
Examples of the condensed aromatic hydrocarbon ring include naphthalene, anthracene, phenanthrene, and the like.
Examples of the monocyclic heteroaromatic ring include pyridine, pyrimidine, pyridazine, and quinoline. Examples of the condensed heteroaromatic ring include quinoxaline, phenanthroline, carbazole, dibenzofuran, dibenzothiophene, and dibenzosilole. .

In formula (1), X ₁ of the A ring, B X _2, C X ₃ rings rings, are included within each ring structure is a coordinating atom to the metal (M).
Examples of the coordination atom include a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, a phosphorus atom, an arsenic atom, and a selenium atom, and a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom. Are preferable, and a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are more preferable.

〔上記中のＲおよび＊は前記と同様の意味を表す。〕
Specific examples of the B ring include the following aromatic hydrocarbon rings.

[R and * in the above represent the same meaning as described above. ]

〔上記式中 Ｒ、*は前記と同じ意味を表す。〕 Moreover, the following are illustrated as a heteroaromatic ring as a specific example of B ring (B13-B62).

[Wherein R and * represent the same meaning as described above. ]

Specific examples of the A ring and the C ring include groups in which one of the bonds in each of the B ring specific examples is substituted with the substituent R.

In Formula (1), m and n each independently represent 0 or 1, and f and g each independently represent an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents an alkynylene group, and the carbon atom of the alkylene group, the alkenylene group and the alkynylene group may be substituted with an oxygen atom or a sulfur atom, respectively.

Examples of the alkylene group having 1 to 6 carbon atoms include —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, and —C ₄ H ₈ —. Examples of the carbon atom (part of which) is substituted with oxygen include —OCH ₂ — and —CH ₂ OC ₂ H ₄ —, and the carbon atom (part of) is substituted with sulfur. Examples thereof include —SCH ₂ — and —CH ₂ SC ₂ H ₄ —.

Examples of the alkenylene group having 1 to 6 carbon atoms include —CH═CH—CH ₂ —, —CH═CH—C ₂ H ₄ —, and —CH ₂ —CH═CH—C ₂ H ₄ —. An example in which (a part of) a carbon atom is substituted with oxygen is —CH═CH—CH ₂ O—, and an example in which (a part of) a carbon atom is substituted with sulfur is —CH = CH-CH ₂ S-.

Examples of the alkynylene group having 1 to 6 carbon atoms include —C≡C—CH ₂ —, —C≡C—C ₂ H ₄ —, and —CH ₂ —C≡C—C ₂ H ₄ —. Examples of the carbon atom (part of which) is substituted with oxygen include —CH≡CH—CH ₂ O—, and the carbon atom (part of) of which is substituted with sulfur include
-CH≡CH-CH ₂ S-
Can be given.

The following are illustrated as a tridentate ligand of the said Formula (1).

〔上記式中 Ｒ、*は前記と同じ意味を表す。〕

[Wherein R and * represent the same meaning as described above. ]

From the viewpoint of synthesis, the A ring, the B ring, and the C ring are preferably monocyclic aromatic hydrocarbon rings or monocyclic heterocycles.

Next, the metal complex having the structure of the formula (2) will be described.
In the formula (2), M is a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au, and a lanthanoid. Specific examples thereof include Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Os, Ir, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu are examples. From the viewpoint of obtaining high efficiency, Ru, Rh, W, Os, Ir, Au, Eu, and Tb are preferable. W, Os, Ir and Au are preferable, W and Au are more preferable, and Au is most preferable.

In the formula (2), the D ring and the E ring each independently represent an aromatic ring, and X ₂ , Y _2, and Z ₂ present in each ring structure are each independently a coordination atom to the metal M H represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, or an alkynylene group having 1 to 6 carbon atoms, and the carbon atoms of the alkylene group, the alkenylene group and the alkynylene group are respectively It may be substituted with an oxygen atom or a sulfur atom, and o represents 0 or 1.
Here, the definition and specific examples of the aromatic ring, the alkylene group having 1 to 6 carbon atoms, the alkenylene group having 1 to 6 carbon atoms or the alkynylene group having 1 to 6 carbon atoms are those definitions and specific examples in the formula (1). It is the same.

〔上記式中 Ｒ、*は前記と同じ意味を表す。〕 Examples of the D ring include the following, but a condensed ring is preferable from the viewpoint of the stability of the complex.

[Wherein R and * represent the same meaning as described above. ]

Specific examples of the E ring include a group in which one of the above-mentioned bonds of B1 to B62 is substituted with a substituent R. From the viewpoint of synthesis, the E ring is a monocyclic aromatic hydrocarbon ring or A monocyclic heterocyclic ring is preferable.

The following are illustrated as a tridentate ligand of the said Formula (2).

Next, the metal complex having the structure of formula (3) will be described. In formula (3), M is a transition metal of the fourth and fifth periods and a metal selected from W, Os, Ir, Au and lanthanoid, Specific examples include Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Os, Ir , Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu are examples. From the viewpoint of obtaining high efficiency, Ru, Rh, W, Os, Ir, Au, Eu and Tb are preferred, W, Os, Ir and Au are more preferred, W and Au are more preferred, and Au is most preferred.

Ring F represents an aromatic ring,
X ₃ , Y ₃ and Z ₃ present in each ring structure each independently represent a coordination atom to the metal M.
Here, definitions and specific examples of the aromatic ring are the same as those definitions and specific examples in the formula (1).

  Specific examples of the F ring, that is, the tridentate ligand of the above formula (3) include the following, and a condensed ring is preferred from the viewpoint of the stability of the complex.

上記式中Ｒ、*は前記と同じ意味を表す。

In the above formula, R and * represent the same meaning as described above.

The metal complex compound having the structure of the above formulas (1) to (3) may have two tridentate ligands, or two in addition to one tridentate ligand and a monodentate ligand. It may have a bidentate ligand.
The bidentate ligand is not particularly limited. For example, phenylpyridine, phenanthroline, phenylquinoline or bidentate coordination described in JP-T-2003-515897 which may be substituted with an alkyl group or a halogen atom. Child etc. are mentioned.

The light emission from the metal complex of the present invention is not particularly limited, but it is preferable in view of obtaining high efficiency that light emission from an MLCT excited state (Metal to Ligand charge transfer excited state) is included.

The metal complex of the present invention preferably exhibits photoluminescence in the visible region at 10 ° C. or higher, and more preferably exhibits electroluminescence in the visible region at 10 ° C. or higher.

Next, a method for synthesizing the metal complex of the present invention will be described.
For metal halides and their hydrates that can be stably obtained, the metal salt and ligand are heated with an appropriate solvent such as alcohol to remove HX (X = metal salt represented by ortho metalation reaction). It is possible to synthesize M (L ₁ ) (L ₂ ), which is an intermediate, by a (halogen ion derived) reaction. Here, L ₁ represents the tridentate ligand described above, and L ₂ represents a halogen ion derived from a metal salt. For example, the method described in Non-Patent Document 3 is exemplified as the synthesis method.
The same reaction can be applied not only to metal halides but also to general metal salts such as acetates, nitrates, sulfates and perchlorates.
In addition to a method for synthesizing an intermediate by orthometalation of a metal halide, a synthesis method by oxidative addition of a ligand to a low-valent metal is also possible. That is, assuming that the valence n of the metal ion of the intermediate M (L ₁ ) (L ₂ ) is M (L ₁ ) by an oxidative addition reaction using (n-2) -valent metal M ′ and L ₁ -Z. (Z) can be obtained. Here, the metal M ′ may have a substitution active ligand such as phosphine or carbonyl, and Z represents a substituent that easily undergoes oxidative addition such as bromine or iodine, and binds to the metal on L _1. Assume that the position is replaced. Since Z is a substitution active ligand similar to L ₂ , the obtained M ′ (L ₁ ) (Z) can also be used as an intermediate in the present invention.
It is possible to convert a halogen ligand into the monodentate ligand by a ligand exchange reaction in a suitable organic solvent for the raw material M (L ₁ ) (L ₂ ). All the reactions shown here are usually carried out in an organic solvent. Examples of the solvent include ether solvents such as diethyl ether, tetrahydrofuran, tertiary butyl methyl ether and dioxane, hexane, cyclohexane, toluene and xylene. Hydrocarbon solvents, ester solvents such as ethyl acetate, propionic acid methyl ester, halogen solvents such as dichloromethane, chloroform, 1,2-dichloroethane, ketone solvents such as acetone, methyl isobutyl ketone, diethyl ketone, Alcohol solvents such as ethanol, butanol, ethylene glycol, and glycerin are used. Although the usage-amount of a solvent is not restrict | limited in particular, Usually, it is about 10 to 500 times in a weight ratio with respect to the total weight of the complexes and ligands which are a raw material.

Although reaction temperature is not specifically limited, Usually, it can be made to react between melting | fusing point of a solvent and a boiling point, -78 degreeC-the boiling point of a solvent is preferable.
The reaction time is not particularly limited, but is usually about 30 minutes to 30 hours.

  As a synthesis operation, a solvent is put into a flask and stirred, and deaerated by bubbling with an inert gas such as nitrogen gas or argon gas, and then a complex and a ligand are added. While stirring, the temperature is raised to a temperature at which the ligand is exchanged in an inert gas atmosphere, and the mixture is kept warm. The end point of the reaction can be determined by stopping the decrease of the raw material by TLC monitor or high performance liquid chromatography or disappearance of either raw material.

  Extraction and purification of the target product from the reaction mixture vary depending on the complex, and ordinary complex purification techniques are used.

For example, a 1N aqueous hydrochloric acid solution, which is a poor solvent for the complex, is added to precipitate the complex, which is filtered off and this solid is dissolved in an organic solvent such as dichloromethane or chloroform. This solution is filtered to remove insolubles, concentrated again, and purified by silica gel column chromatography (elution with dichloromethane) .The fraction solution of the desired product is collected, and for example, an appropriate amount of methanol (poor solvent) is added and concentrated. The target complex is precipitated, filtered and dried to obtain the complex.
The compound can be identified and analyzed by CHN elemental analysis and NMR.

The composition of the present invention contains the metal complex of the present invention and an organic compound.

The composition of the present invention represents, for example, a mixture of other organic compounds as a host compound. Examples of the host compound include low molecular weight host compounds for metal complex phosphorescent compounds and polymers known so far. Can be mentioned.
Specific examples of the low molecular weight host compound include the following compounds.

A polymer can also be used as the host compound. Examples of the polymer include non-conjugated polymers and conjugated polymers. Examples of the nonconjugated polymer include polyvinyl carbazole. Examples of the conjugated polymer include a polymer containing an aromatic ring in the main chain, and more specifically, a polymer containing the following structure.

The polymer used as the host may be a copolymer containing the above structure or a polymer composition.

The number average molecular weight in terms of polystyrene of the polymer used in the composition of the present invention is preferably 10 ³ to 10 ⁸ , more preferably 10 ⁴ to 10 ⁶ . The weight average molecular weight in terms of polystyrene is 10 ³ to 10 ⁸ , preferably 5 × 10 ^{4 to} 5 × 10 ⁶ .
Moreover, the metal complex of the present invention may be incorporated as a partial structure in the polymer.
That is, the present invention relates to a polymer metal complex containing in its molecule the structure of the metal complex of the present invention.

Examples of the polymer into which the metal complex is incorporated include the polymers described above as the polymer used as the composition of the present invention.

The amount of the metal complex in the composition of the present invention varies depending on the type of organic compound to be combined and the property to be optimized, and is not particularly limited. However, when the amount of the organic compound is 100 parts by weight, it is usually 0.01 to 80. Parts by weight, preferably 0.1 to 60 parts by weight. Two or more kinds of metal complexes may be included.

The composition of the present invention may further contain at least one material selected from a hole transport material, an electron transport material and a light emitting material.

Examples of the hole transport material include aromatic amines, carbazole derivatives, polyparaphenylene derivatives, and the like that have been used as hole transport materials in organic EL devices so far.

In addition, as an electron transport material, an oxadiazole derivative anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative, which has been used as an electron transport material in an organic EL device until now. Derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, poly Examples include fluorene or a derivative thereof.

  A well-known thing can be used as a luminescent material. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

As an ink composition (for example, used as a solution in a printing method or the like), it is sufficient that at least one metal complex or composition of the present invention is contained.
In addition to the metal complex or composition of the present invention, the ink composition usually contains a solvent, and controls the hole transport material, electron transport material, light emitting material, stabilizer, viscosity and / or surface tension. Additives such as additives and antioxidants may be included.
The ratio of the metal complex or the composition of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the ink composition excluding the solvent. is there.
The proportion of the solvent in the ink composition is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.9 wt%, more preferably 90 wt% to 99.99 wt% with respect to the total weight of the ink composition. 8 wt%.
Although the viscosity of the ink composition varies depending on the printing method, the range is 0.5 to 500 mPa · s at 25 ° C., preferably 1 to 100 mPa · s. The ink composition such as the ink jet printing method passes through the ejection device. In the case of a thing, in order to prevent the clogging at the time of discharge and a flight bending, it is preferable that a viscosity is the range of 1-20 mPa * s in 25 degreeC.

  As the solvent used in the ink composition, those capable of dissolving or uniformly dispersing the metal complex or the composition of the present invention are preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, trimethylbenzene, Aromatic hydrocarbon solvents such as mesitylene, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, aliphatic hydrocarbon solvents such as n-decane, acetone, Ketone solvents such as methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ether Polyhydric alcohols such as lenglycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and their derivatives, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination. Of the above solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring, a melting point of 0 ° C. or lower, and a boiling point of 100 ° C. or higher.

  Examples of the solvent include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and the like from the viewpoint of solubility in the organic solvent of the metal complex or composition of the present invention, uniformity during film formation, viscosity characteristics, and the like. Ester solvents and ketone solvents are preferred, and toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole, Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent in the ink composition is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics. .

  When the ink composition contains two types of solvents, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one type of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and the other one type of solvent is preferably a solvent having a boiling point of 180 ° C. or lower. It is more preferable that the solvent is a solvent having a boiling point of 180 ° C. or lower. Further, from the viewpoint of viscosity, it is preferable that 0.2 wt% or more of the metal complex or composition of the present invention is dissolved at 60 ° C. in one of the two solvents. It is preferable that 0.2 wt% or more of the metal complex or composition of the present invention dissolves at 25 ° C.

  When the ink composition contains three types of solvents, one or two of them may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. Further, from the viewpoint of viscosity, it is preferable that 0.2 wt% or more of the metal complex or the composition of the present invention is dissolved in two of the three solvents at 60 ° C. It is preferable that 0.2 wt% or more of the metal complex or composition of the present invention is dissolved in one kind of solvent at 25 ° C.

  When the ink composition contains two or more kinds of solvents, the solvent having the highest boiling point is preferably 40 to 90 wt% of the total solvent weight of the ink composition from the viewpoint of viscosity and film formability. More preferably, it is -90 wt%, and it is further more preferable that it is 65-85 wt%.

  The ink composition of the present invention includes, from the viewpoint of viscosity and film formability, a composition composed of anisole and bicyclohexyl, a composition composed of anisole and cyclohexylbenzene, a composition composed of xylene and bicyclohexyl, and xylene and cyclohexylbenzene. A composition consisting of mesitylene and methyl benzoate is preferred.

Among the additives that the ink composition of the present invention can contain,
As the hole transport material, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, a polyaniline or Examples thereof include polythiophene or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-thienylenevinylene) or a derivative thereof.
Electron transport materials include oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinodimethane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene Alternatively, a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof can be given.
Examples of the light-emitting material include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its metal complexes, aromatic amines, tetra Examples thereof include phenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof.
Examples of the stabilizer include phenolic antioxidants and phosphorus antioxidants.
Additives for adjusting viscosity and / or surface tension include high molecular weight compounds (thickeners) to increase viscosity, poor solvents, low molecular weight compounds to reduce viscosity, and surface tension to lower Therefore, the surfactants and the like may be used in appropriate combination.

  The high molecular weight polymer compound may be any compound that is soluble in the same solvent as the metal complex or composition of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a polymer compound of the present invention having a high molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and amount of the solvent may be selected as long as the solid content in the solution does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50 wt% or less, more preferably 30 wt% or less with respect to the entire solution.

The antioxidant is not particularly limited as long as it is soluble in the same solvent as the metal complex or composition of the present invention and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants. . By using an antioxidant, the storage stability of the metal complex or composition of the present invention and the solvent can be improved.

  From the viewpoint of the solubility of the metal complex or composition of the present invention in a solvent, the difference between the solubility parameter of the solvent and the solubility parameter of the polymer compound is preferably 10 or less, more preferably 7 or less. preferable.

The solubility parameter of the solvent and the solubility parameter of the metal complex or composition of the present invention can be determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

  The metal complex of the present invention contained in the ink composition may be one type or two or more types, and may contain a polymer compound other than the metal complex of the present invention as long as device characteristics and the like are not impaired.

Note that the metal complex used in the present invention can be used not only as a light emitting material, but also as an organic semiconductor material, an optical material, or a conductive material by doping.

  Next, the element of the present invention will be described. The element of the present invention is characterized by having a layer containing the metal complex of the present invention or the composition of the present invention between electrodes composed of an anode and a cathode, and can be used as, for example, a photoelectric element or a light emitting element. When the element is a light emitting element, the layer containing the metal complex of the present invention is preferably a light emitting layer.

The light emitting device of the present invention may further include a charge transport layer or a charge blocking layer between electrodes composed of an anode and a cathode. The charge transport layer means a hole transport layer or an electron transport layer, and the charge blocking layer means a hole blocking layer or an electron blocking layer. A light emitting device in which an electron transport layer or a hole blocking layer is provided between a cathode and a light emitting layer, a light emitting device in which a hole transport layer or an electron blocking layer is provided between an anode and a light emitting layer, a cathode and a light emitting layer And a light-emitting element in which an electron transport layer or a hole blocking layer is provided between the anode and the light emitting layer, and a hole transport layer or an electron blocking layer is provided between the anode and the light emitting layer. Here, the electron transport layer and the hole blocking layer have the same function as described in “All about organic EL” page 162 (Koji Koji, Nihon Jitsugyo Shuppan), for example, the electron transport layer and the hole blocking layer. The same material can be used, and either function may be more strongly reflected depending on the characteristics of the material. The same applies to the hole transport layer and the electron blocking layer. Examples of the light-emitting element of the present invention include a patent document (Journal of the SID 11/1, 161-166, 2003).
An example of the element structure described in FIG.
A light emitting element provided with a layer containing a conductive polymer adjacent to the electrode between the at least one electrode and the light emitting layer; adjacent to the electrode between the at least one electrode and the light emitting layer Examples include a light emitting element provided with a buffer layer having an average film thickness of 2 nm or less.

Specifically, the following structures a) to d) are exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, that is, a light emitting thin film, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer transports electrons. It is a layer having the function of The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer.
Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  In addition, in order to improve adhesion with the electrode or improve charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode. In order to improve or prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  Further, a hole blocking layer may be inserted at the interface with the light emitting layer in order to transport electrons and confine holes.

  The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

  In the present invention, as a light emitting device provided with a charge injection layer (electron injection layer, hole injection layer), a light emitting device provided with a charge injection layer adjacent to the cathode, and a charge injection layer provided adjacent to the anode. A light emitting element is mentioned.

For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / charge transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.

Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.

  The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polyaminophen and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene Examples include vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), carbon, etc. The

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As a light emitting element provided with an insulating layer having a thickness of 2 nm or less, a light emitting element provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, or a light emitting element provided with an insulating layer having a thickness of 2 nm or less adjacent to the anode Is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The hole blocking layer has a function of transporting electrons and confining holes transported from the anode, and is provided at an interface on the cathode side of the light emitting layer, and has an ionization potential larger than the ionization potential of the light emitting layer. For example, a metal complex of bathocuproine, 8-hydroxyquinoline or a derivative thereof.

  The film thickness of the hole blocking layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

Specifically, for example, the following structures ac) to an) are mentioned.
ac) anode / charge injection layer / light emitting layer / hole blocking layer / cathode ad) anode / light emitting layer / hole blocking layer / charge injection layer / cathode ae) anode / charge injection layer / light emitting layer / hole blocking layer / Charge injection layer / cathode af) anode / charge injection layer / hole transport layer / light emitting layer / hole blocking layer / cathode ag) anode / hole transport layer / light emitting layer / hole blocking layer / charge injection layer / cathode ah ) Anode / charge injection layer / hole transport layer / light emitting layer / hole blocking layer / charge injection layer / cathode ai) anode / charge injection layer / light emitting layer / hole blocking layer / charge transport layer / cathode aj) anode / Light emitting layer / hole blocking layer / electron transport layer / charge injection layer / cathode ak) anode / charge injection layer / light emitting layer / hole blocking layer / electron transport layer / charge injection layer / cathode al) anode / charge injection layer / Hole transport layer / light emitting layer / hole blocking layer / charge transport layer / cathode am) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer Charge injection layer / cathode an) anode / charge injection layer / hole transport layer / luminescent layer / hole blocking layer / electron transport layer / charge injection layer / cathode

  When the light emitting material including the host is formed into a film from the solution when the light emitting device of the present invention is produced, it is only necessary to remove the solvent by drying after applying the solution, and the charge transporting material and the light emitting material are mixed. In this case, the same technique can be applied, which is very advantageous in manufacturing. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. When the film is formed by a printing method or the like, it can be formed using the ink composition. In the case where the light emitting material including the host has a relatively low molecular weight, the light emitting layer may be formed using a vacuum deposition method.

  In the light emitting device of the present invention, a light emitting material other than the metal complex or composition of the present invention may be mixed and used in the light emitting layer. In the light emitting device of the present invention, a light emitting layer containing a light emitting material other than the present invention may be laminated with a light emitting layer containing the metal complex or composition of the present invention.

  As the light emitting material, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

  Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

  When the light-emitting element of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, Pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polyaminophen or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polyaminophen or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof. , Polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989) and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the light-emitting device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinones or derivatives thereof, naphthoquinones or derivatives thereof. , Anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof Examples thereof include a derivative, polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  These aminoxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinone or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, and for polymer electron transport materials, solution or Each method is exemplified by film formation from a molten state. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polyaminophen or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The substrate for forming the light emitting device of the present invention may be any substrate as long as it forms an electrode and does not change when each layer of the polymer LED is formed. Examples thereof include glass, plastic, polymer film, and silicon substrate. The In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, it is preferable that at least one of the electrodes composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent.
As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. In addition, an organic transparent conductive film such as polyaniline or a derivative thereof, polyaminophen or a derivative thereof may be used as the anode.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

  Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material for the cathode used in the light emitting device of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.

  The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, metal fluoride, organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic layer. A protective layer for protecting the light emitting element may be attached. In order to use the light-emitting element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

The metal complex or composition of the present invention can also be used as a conductive material or a semiconductor material. A conductive thin film or an organic semiconductor thin film can be formed into an element by a method similar to the method for manufacturing a light-emitting element described above, and the semiconductor thin film has a higher electron mobility or hole mobility. Preferably, it is 10 ⁻⁵ cm ² / V / second or more.

  The organic semiconductor thin film can be used for organic solar cells and organic transistors.

  The light emitting element of the present invention can be used for a planar light source, a segment display device, a dot matrix, a backlight or illumination of a liquid crystal display device.

  In order to obtain planar light emission using the light emitting element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of light emitting materials having different emission colors or a method using a color filter or a light emission conversion filter. The dot matrix element can be driven passively, or can be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

Next, as another aspect of the present invention, a photoelectric element will be described.
As the photoelectric element, for example, there is a photoelectric conversion element, at least one of which is transparent or semitransparent, an element in which a layer containing the metal complex or composition of the present invention is sandwiched, or a film formed on a substrate Examples include a device having a comb-shaped electrode formed on a layer containing the polymer compound or polymer composition of the present invention. In order to improve the characteristics, fullerene, carbon nanotube, or the like may be mixed.
As a manufacturing method of a photoelectric conversion element, the method described in Japanese Patent No. 3146296 is exemplified. Specifically, a method of forming a polymer thin film on a substrate having a first electrode and forming a second electrode thereon, a polymer thin film on a pair of comb-shaped electrodes formed on the substrate The method of forming is illustrated. One of the first and second electrodes is transparent or translucent.
Although there is no restriction | limiting in particular about the formation method of a polymer thin film, and the method of mixing fullerene and a carbon nanotube, What was illustrated by the light emitting element can be utilized suitably.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

Here, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC: HLC-8220GPC, manufactured by Tosoh or SCL-10A, manufactured by Shimadzu Corporation) using tetrahydrofuran as a solvent.

化合物（Ｍ−１）はＯｒｇａｎｏｍｅｔａｌｌｉｃｓ；１９９８，１７，３５０５−３５１１．記載の方法で合成した。


上記化合物（Ｍ−１）の０．８ｗｔ％クロロホルム溶液を石英板上に１６００ｒｐｍで６０秒間、スピンコートして薄膜を作製した。室温下でＰＬ測定を行ったが発光スペクトルは観測できなかった。

化合物（Ｍ−２）

Example 1 Synthesis of Compound (M-2) Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in an argon atmosphere, washed with hexane, and decanted. The supernatant was removed. To this was added dehydrated THF (20 ml) and then carbazole (72 mg, 0.43 mmol), and the mixture was stirred at room temperature for 30 minutes. After confirming that the generation of hydrogen was completed by visual observation, Compound (M-1) (200 mg, 0.43 mmol) was added and stirred at room temperature. Although it is suspended at the start of the reaction, it becomes an orange solution after about 1 hour. After further stirring at room temperature for about 1 hour, the solvent was distilled off under reduced pressure. The resulting solid was dissolved in chloroform (100 ml) and passed through a short column of alumina. The fraction was concentrated under reduced pressure, and an appropriate amount of hexane was added to recrystallize to obtain a red powdery compound (M-2) (216 mg).
¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ 6.80 (d, 2H), 7.12-7.39 (m, 8H), 7.54 (d, 2H), 7.68 (d, 2H) ), 7.73 (d, 2H), 8.08 (t, 1H), 8.24 (d, 2H).
MS (ESI-positive) m / z: 594.1 ([M + H] ^< +>).


A 0.8 wt% chloroform solution of the following compound (M-2) was spin-coated on a quartz plate at 1500 rpm for 60 seconds to produce a thin film. By measuring PL of the fluorescence spectrum of this thin film using a fluorescence spectrophotometer (Fluorolog manufactured by JOBINYVON-SPEX) at an excitation wavelength of 350 nm and room temperature, PL emission having a peak at 575 nm in the emission spectrum was observed.

Compound (M-1)

Compound (M-1) is Organometallics; 1998, 17, 3505-3511. Synthesized by the method described.


A 0.8 wt% chloroform solution of the above compound (M-1) was spin-coated on a quartz plate at 1600 rpm for 60 seconds to produce a thin film. PL measurement was performed at room temperature, but no emission spectrum could be observed.

Compound (M-2)

Example 2 Synthesis of Compound (M-3) Pentafluorophenyl magnesium bromide was prepared by reacting magnesium and bromopentafluorobenzene in THF in an argon atmosphere and used as it was. Under an argon atmosphere, the compound (M-1) (400 mg, 0.86 mmol) was weighed into a 100 mL three-necked flask, and dehydrated THF (40 ml) was added. While the obtained suspension was cooled with water, the pentafluorophenyl magnesium bromide THF solution (1M, 1.3 ml, 1.3 mmol) was added dropwise with a syringe. After dropping, the solution was stirred at room temperature for 1 hour to obtain a colorless solution. After stirring for a while, the solvent was distilled off under reduced pressure, the complex was dissolved in chloroform and passed through a short column of alumina. The yellow fraction developed first and the colorless fraction developed next were separated, and the compound (M-3) was obtained from the colorless fraction (300 mg).
¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ 7.19 (d, 2H), 7.31-7.35 (m, 4H), 7.62 (d, 2H), 7.70 (dd, 2H) ), 8.01 (dd, 1H).


A 0.8 wt% chloroform solution of the following compound (M-3) was spin-coated on a quartz plate at 1600 rpm for 60 seconds to produce a thin film. By measuring PL at room temperature, PL emission having peaks at 479 nm and 510 nm in the emission spectrum was observed.

(Compound M-3)

Example 3
A 0.8 wt% chloroform solution of a mixture obtained by adding 2 wt% of the compound (M-2) to the following compound (M-4) was prepared.
A glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method was formed into a film having a thickness of 80 nm by spin coating using a solution of poly (ethylenedioxyaminophene) / polystyrenesulfonic acid (Bayer, BaytronP), Dried for 10 minutes at 200 ° C. on a hot plate. Next, a film was formed at a rotational speed of 3000 rpm by spin coating using the prepared chloroform solution. The film thickness was about 100 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
By applying a voltage to the obtained device at room temperature, EL emission having a peak at 575 nm in the emission spectrum was obtained. The EL characteristics were measured by OLED TEST SYSTEM (manufactured by Tokyo System Development Co., Ltd.).

(Compound M-4)

Example 4
A 0.8 wt% chloroform solution of a mixture obtained by adding 2 wt% of the compound (M-3) to the compound (M-4) was prepared, and an EL device was produced in the same manner as described in Example 3 using this solution.
By applying voltage to the obtained device at room temperature, EL light emission having peaks at 480 and 510 nm in the emission spectrum was obtained. The EL characteristics were measured by OLED TEST SYSTEM (manufactured by Tokyo System Development Co., Ltd.).

Example 5
A 0.6 wt% chloroform solution of a mixture obtained by adding 5 wt% of the compound (M-3) to the polymer compound (P-1) is prepared, and an EL device is produced in the same manner as described in Example 3 using this solution. did.
By applying a voltage to the obtained device at room temperature, EL light emission having a peak at 580 nm in the emission spectrum was obtained. The EL characteristics were measured by OLED TEST SYSTEM (manufactured by Tokyo System Development Co., Ltd.).
The polymer compound (P-1) was synthesized by the method described in EP 1344788 (polystyrene equivalent number average molecular weight was Mn = 1.1 × 10 ⁵ , and weight average molecular weight was Mw = 2.7 × 10 ^5. ).

Polymer compound (P-1)

[Comparative Example 1]
A 0.6 wt% THF solution of a mixture obtained by adding 5 wt% of the compound (M-1) to the polymer compound (P-1) was prepared.
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 80 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotational speed of 2000 rpm by spin coating using the prepared THF solution. The film thickness was about 70 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started. Although voltage was applied to the obtained device up to 20 V, light emission from the compound (M-1) was not observed.

Example 6 Synthesis of Compound (M-5) Sodium hydride (60 wt% in mineral oil, 87 mg, 2.17 mmol) was weighed into a 100 mL three-necked flask in an argon atmosphere, washed with hexane, and decanted. The supernatant was removed. Dehydrated THF (200 ml) and then 2,7-dibromocarbazole (704 mg, 2.17 mmol) were added thereto, followed by stirring at room temperature for 30 minutes. After confirming that the generation of hydrogen was completed by visual observation, Compound (M-1) (1.0 g, 2.17 mmol) was added and stirred at room temperature. Although it is suspended at the start of the reaction, it becomes an orange solution after about 1 hour. Furthermore, after stirring at room temperature for about 1 hour, the solvent was distilled off under reduced pressure, and the resulting solid was dissolved in dichloromethane (300 ml), followed by celite filtration. The compound (M-5) was obtained by recrystallizing an appropriate amount of hexane (1.3 g).
¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ 6.74 (d, 2H), 7.17 (dd, 2H), 7.32 (m, 4H), 7.68 (m, 6H), 8. 09 (dd, 3H).
MS (ESI-positive) m / z: 594.1 ([M + H] ^< +>).

Compound (M-5)

[Example 7] Synthesis of polymer compound (P-2) 25 mg (0.033 mmol) of the above compound (M-5), 475 mg (0.82 mmol) of 2,7-dibromo-3,6-octyloxydibenzofuran, 2 , 2′-bipyridyl (351 mg) was charged into a reaction vessel, and the reaction system was replaced with nitrogen gas. To this, 35 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 630 mg of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this mixed solution, stirred at room temperature for 30 minutes, and then reacted at 60 ° C. for 3.3 hours. . The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled and then poured into a mixed solution of 15 ml of methanol / 15 ml of ion-exchanged water / 2.5 ml of 25% aqueous ammonia and stirred for about 2 hours. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in toluene. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column filled with alumina. Next, this solution was washed with 1N hydrochloric acid, 2.5% ammonia water, and ion exchange water, poured into methanol, re-precipitated, and the produced precipitate was recovered. This precipitate was dried under reduced pressure to obtain 120 mg of polymer (P-2).
This polymer had a polystyrene equivalent number average molecular weight of 2.6 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 4.5 × 10 ⁴ .
In addition, 2,7-dibromo-3,6-octyloxydibenzofuran was synthesized by the method described in EP 1344788.

[Example 8] Synthesis of polymer compound (P-3) 50 mg (0.067 mmol) of the above compound (M-5), 450 mg (0.77 mmol) of 2,7-dibromo-3,6-octyloxydibenzofuran, 2 , 2′-bipyridyl (354 mg) was charged into the reaction vessel, and the reaction system was replaced with nitrogen gas. To this, 35 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 623 mg of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this mixed solution, stirred at room temperature for 30 minutes, and then reacted at 60 ° C. for 3.3 hours. . The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled and then poured into a mixed solution of 15 ml of methanol / 15 ml of ion-exchanged water / 2.5 ml of 25% aqueous ammonia and stirred for about 2 hours. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in toluene. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column filled with alumina. Next, this solution was washed with 1N hydrochloric acid, 2.5% ammonia water, and ion exchange water, poured into methanol, re-precipitated, and the produced precipitate was recovered. This precipitate was dried under reduced pressure to obtain 116 mg of polymer (P-2).
This polymer had a polystyrene-reduced number average molecular weight of 3.0 × 10 ⁴ and a polystyrene-reduced weight average molecular weight of 4.8 × 10 ⁴ .

Example 9
A 2 wt% toluene solution of the polymer compound (P-3) was prepared.
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 80 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotational speed of 600 rpm by spin coating using a 2 wt% toluene solution of the polymer compound (P-3) prepared above. The film thickness was about 80 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started. By applying a voltage to the obtained device at room temperature, EL emission having a peak at 460 nm in the emission spectrum was obtained. The EL characteristics were measured by OLED TEST SYSTEM (manufactured by Tokyo System Development Co., Ltd.).

Example 10
Using the polymer compound (P-3), a device in which a hole current mainly flows was produced. The element was produced as follows.
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 80 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotational speed of 2800 rpm by spin coating using a 1.7 wt% toluene solution of the polymer compound (P-3). The film thickness was about 80 nm. Furthermore, after drying this at 80 degreeC under pressure reduction for 1 hour, about 100 nm of Au was vapor-deposited as a cathode buffer layer, and the element was produced. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
The current densities when voltages of 5 V and 10 V were applied to the fabricated devices were 2.0 × 10 ⁻⁵ A / cm ² and 4.4 × 10 ⁻⁵ A / cm ² , respectively. The current density was measured using a Picoammeter 4140B (manufactured by Yokogawa Hewlett-Packard Company).

[Comparative Example 2]
For comparison, a similar device was produced using the above polymer compound (P-1) that does not contain a metal complex structure. The current densities when a voltage of 5 V or 10 V was applied to the fabricated devices were 3.1 × 10 ⁻⁶ A / cm ² and 8.7 × 10 ⁻⁶ A / cm ² , respectively. 3) showed better hole current injection characteristics and transportability.

Claims (22)

It has a metal selected from W, Os, Ir and Au, a monodentate ligand, and a tridentate ligand containing one or more aromatic rings and containing three coordination atoms in the aromatic ring structure A metal complex that emits light in the visible region above 10 ° C,
A structure the single dentate ligand is selected structures or we shown below,

[In the above formula , * represents an atom coordinated to a metal, and R is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, silyl group, Ha androgenic atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, carboxyl Motoma other a cyano group. ]
A metal complex, wherein the tridentate ligand is a structure selected from the structures shown below.

[Wherein R and * represent the same meaning as described above. ] The metal complex according to claim 1, wherein the metal is W or Au. A composition comprising the metal complex according to claim 1 or 2 and an organic compound. The composition according to claim 3, wherein the organic compound is a conjugated polymer. The composition according to claim 3 or 4 , further comprising at least one material selected from a hole transport material, an electron transport material, and a light emitting material. An ink composition comprising at least one of the metal complex according to claim 1 or 2 or the composition according to any one of claims 3 to 5 . The ink composition according to claim 6, comprising two or more organic solvents. The ink composition according to claim 6 or 7 , wherein the viscosity is 1 to 100 mPa · s at 25 ° C. Light-emitting thin film comprising the composition of any one of metal complexes or claim 3-5 according to claim 1 or 2. Conductive thin film comprising the composition of any of claims 1 or metal complex according to 2 or Claim 3-5. An organic semiconductor thin film containing the metal complex according to claim 1 or 2 or the composition according to any one of claims 3 to 5 . An organic transistor comprising the organic semiconductor thin film according to claim 11 . The method for producing a thin film according to any one of claims 9 to 12, wherein an inkjet method is used. A device comprising a layer containing the metal complex according to claim 1 or 2 or the composition according to any one of claims 3 to 5 between electrodes comprising an anode and a cathode. The device according to claim 14 , further comprising a charge transport layer or a charge blocking layer between the electrodes composed of an anode and a cathode. Between electrodes consisting of an anode and a cathode that has an organic layer, the organic layer is a light emitting layer comprising the composition of any of metal complexes or claim 3-5 according to claim 1 or 2 A light emitting device characterized by the above. The light emitting device according to claim 16 , wherein the light emitting layer further contains at least one material selected from a hole transport material, an electron transport material and a light emitting material. Planar light source characterized by using the light-emitting device according to claim 16 or 17. Segment display device characterized by using the light-emitting device according to claim 16 or 17. Dot matrix display device characterized by using the light-emitting device according to claim 16 or 17. The liquid crystal display device, characterized by a backlight light-emitting device according to claim 16 or 17. Illumination characterized by using the light-emitting device according to claim 16 or 17.