JP2015174824A - Metal complex and light emitting element prepared using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal complex useful for producing a light emitting element having excellent drive voltage.SOLUTION: This invention provides a metal complex represented by formula (1) where any of R, R, Rand Ris a group or the like represented by formula (D-A).

Description

  The present invention relates to a metal complex, a composition containing the metal complex, and a light-emitting element obtained using the metal complex.

  As a light-emitting material used for a light-emitting layer of a light-emitting element, a phosphorescent compound or the like that emits light from a triplet excited state has been studied. For example, Patent Document 1 describes a metal complex A represented by the following formula. Patent Document 2 describes a metal complex B represented by the following formula. These metal complexes are metal complexes in which the ligand has a phenylimidazole structure.

JP 2008-303150 A International Publication No. 2006/121811

  However, a light emitting device manufactured using the above metal complex has a problem of high driving voltage.

  Then, an object of this invention is to provide a metal complex useful for manufacture of the light emitting element which is excellent in a drive voltage. Another object of the present invention is to provide a composition containing the metal complex and a light-emitting device obtained using the metal complex.

  The present invention first provides a metal complex represented by the following formula (1).

［式中、
ｎ_１は、１、２または３を表す。ｎ_２は、０または１を表す。ｎ_２が複数存在する場合、それらは同一でも異なっていてもよい。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基またはハロゲン原子を表し、これらの基は置換基を有していてもよい。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^４とＲ^５、Ｒ^５とＲ^６、Ｒ^７とＲ^８、および、Ｒ^１０とＲ^１１は、それぞれ結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。また、Ｒ^４、Ｒ^８、Ｒ^９およびＲ^１０からなる群から選ばれる少なくとも１つは、下記式（Ｄ−Ａ）または（Ｄ−Ｂ）で表される基である。
Ａ^１−Ｇ^１−Ａ^２は、アニオン性の２座配位子を表し、Ｇ^１は、Ａ^１およびＡ^２とともに２座配位子を構成する原子団を表す。Ａ^１およびＡ^２は、それぞれ独立に、炭素原子、酸素原子または窒素原子を表し、これらの原子は環を構成する原子であってもよい。Ａ^１−Ｇ^１−Ａ^２が複数存在する場合、それらは同一でも異なっていてもよい。］

[Where:
n ₁ represents ₁ , 2 or 3. n ₂ represents 0 or 1. When a plurality of n ₂ are present, they may be the same or different.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group. Represents a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent. When a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are present, they may be the same or different. R ¹ and R ² , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ¹⁰ and R ¹¹ are bonded to each other and bonded to each other. And may form a ring. At least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following formula (DA) or (DB).
A ¹ -G ¹ -A ² represents an anionic bidentate ligand, and G ¹ represents an atomic group constituting a bidentate ligand together with A ¹ and A ² . A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² are present, they may be the same or different. ]

［式中、
ｍ^DA1、ｍ^DA2およびｍ^DA3は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＴ^DAは、同一でも異なっていてもよい。］

[Where:
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDA may be the same or different. ]

［式中、
ｍ^DA1、ｍ^DA2、ｍ^DA3、ｍ^DA4、ｍ^DA5、ｍ^DA6およびｍ^DA7は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＧ^DAは、同一でも異なっていてもよい。
Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3、Ａｒ^DA4、Ａｒ^DA5、Ａｒ^DA6およびＡｒ^DA7は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3、Ａｒ^DA4、Ａｒ^DA5、Ａｒ^DA6およびＡｒ^DA7が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＴ^DAは、同一でも異なっていてもよい。］

[Where:
^{m DA1, m DA2, m DA3} , m DA4, m DA5, m DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent. A plurality of ^GDAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDA may be the same or different. ]

The present invention secondly, the above metal complex,
A composition containing a polymer compound containing a structural unit represented by the following formula (Y), or
The above metal complex;
Provided is a composition containing a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and at least one material selected from the group consisting of a solvent.

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。］

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ]

  Thirdly, the present invention provides a light emitting device obtained by using the above metal complex.

  ADVANTAGE OF THE INVENTION According to this invention, the metal complex useful for manufacture of the light emitting element which is excellent in a drive voltage can be provided. Moreover, according to this invention, the light emitting element obtained using the composition containing this metal complex and this metal complex can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

<Explanation of common terms>
Terms commonly used in this specification have the following meanings unless otherwise specified.

  Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

  The hydrogen atom may be a deuterium atom or a light hydrogen atom.

  In the formula representing the metal complex, the solid line representing the bond with the central metal means a covalent bond or a coordinate bond.

The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .

  The polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or other embodiments.

  The terminal group of the polymer compound is preferably a stable group because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics or the luminance life may be lowered when the polymer compound is used for the production of a light emitting device. It is. The terminal group is preferably a group that is conjugated to the main chain, and examples thereof include a group that is bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.

“Low molecular weight compound” means a compound having no molecular weight distribution and a molecular weight of 1 × 10 ⁴ or less.

  “Structural unit” means one or more units present in a polymer compound.

The “alkyl group” may be linear or branched. The carbon atom number of a linear alkyl group is 1-50 normally without including the carbon atom number of a substituent, Preferably it is 3-30, More preferably, it is 4-20. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, Hexyl, heptyl, octyl, 2-ethylhexyl, 3-propylheptyl, decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-hexyl-decyl, dodecyl, and these And a group in which the hydrogen atom is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, etc., for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, Perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5-di-hexyl group Butylphenyl) propyl group, and a 6-ethyloxy-hexyl group.
The number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30 and more preferably 4 to 20 without including the number of carbon atoms of the substituent.
The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

“Aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an aryl group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-20, More preferably, it is 6-10.
The aryl group may have a substituent, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups Are groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

The “alkoxy group” may be linear or branched. The number of carbon atoms of a linear alkoxy group is 1-40 normally without including the carbon number of a substituent, Preferably it is 4-10. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The alkoxy group may have a substituent, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, And a group substituted with a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
The number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.

The number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 7 to 48, not including the number of carbon atoms of the substituent.
The aryloxy group may have a substituent, for example, a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples include a pyrenyloxy group and a group in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.

“P-valent heterocyclic group” (p represents an integer of 1 or more) is a p-group of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. This means the remaining atomic group excluding the hydrogen atom. Among the p-valent heterocyclic groups, this is an atomic group obtained by removing p hydrogen atoms from an aromatic heterocyclic compound directly bonded to carbon atoms or heteroatoms constituting the ring. A “p-valent aromatic heterocyclic group” is preferable.
“Aromatic heterocyclic compounds” include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosilole, dibenzophosphole A compound in which the heterocycle itself is aromatic, and a heterocycle itself such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran does not exhibit aromaticity, but the aromatic ring is condensed to the heterocycle Means a compound that has been

The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group, and these And a group in which the hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

  “Halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The “amino group” may have a substituent, and a substituted amino group is preferable. As a substituent which an amino group has, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.
Examples of the amino group include dimethylamino group, diethylamino group, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert- Butylphenyl) amino group.

The “alkenyl group” may be linear or branched. The number of carbon atoms of a linear alkenyl group is 2-30 normally without including the carbon atom number of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkenyl group is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of the substituent.
The number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkenyl group and the cycloalkenyl group may have a substituent, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, Examples include a pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and a group in which these groups have a substituent.

The “alkynyl group” may be linear or branched. The carbon atom number of an alkynyl group is 2-20 normally without including the carbon atom of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The alkynyl group and cycloalkynyl group may have a substituent, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- Examples include a pentynyl group, 1-hexenyl group, 5-hexynyl group, and groups in which these groups have a substituent.

The “arylene group” means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an arylene group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-30, More preferably, it is 6-18.
The arylene group may have a substituent, for example, phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, naphthacene diyl group, fluorenediyl group, pyrenediyl group, perylene diyl group, Examples include chrysenediyl groups and groups in which these groups have substituents, and groups represented by formula (A-1) to formula (A-20) are preferable. The arylene group includes a group in which a plurality of these groups are bonded.

［式中、ＲおよびＲ^aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表す。複数存在するＲおよびＲ^aは、各々、同一でも異なっていてもよく、Ｒ^a同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R and R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20 and more preferably 4 to 15 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, Divalent acridine, furan, thiophene, azole, diazole, and triazole include divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring, and preferably Is a group represented by formula (AA-1) to formula (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、ＲおよびＲ^aは、前記と同じ意味を表す。］

[Wherein, R and R ^a represent the same meaning as described above. ]

  The “crosslinking group” is a group capable of generating a new bond by being subjected to heat treatment, ultraviolet irradiation treatment, radical reaction or the like, and preferably has the formula (B-1)-(B-17 ). These groups may have a substituent.

  “Substituent” means a halogen atom, cyano group, alkyl group, cycloalkyl group, aryl group, monovalent heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, amino group, substituted amino group, alkenyl group. Represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substituent may be a crosslinking group.

  “Dendron” means a group having a regular dendritic branched structure (ie, a dendrimer structure) having an atom or a ring as a branching point. Examples of the compound having a dendron (hereinafter referred to as “dendrimer”) include, for example, International Publication No. 02/067343, Japanese Patent Application Laid-Open No. 2003-231692, International Publication No. 2003/079736, International Publication No. 2006/097717. And the structure described in the literature.

  The dendron is preferably a group represented by the formula (D-A) or (D-B).

［式中、
ｍ^DA1、ｍ^DA2およびｍ^DA3は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるＴ^DAは、同一でも異なっていてもよい。］

[Where:
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. The plurality of ^TDAs may be the same or different. ]

［式中、
ｍ^DA1、ｍ^DA2、ｍ^DA3、ｍ^DA4、ｍ^DA5、ｍ^DA6およびｍ^DA7は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。複数あるＧ^DAは、同一でも異なっていてもよい。
Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3、Ａｒ^DA4、Ａｒ^DA5、Ａｒ^DA6およびＡｒ^DA7は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3、Ａｒ^DA4、Ａｒ^DA5、Ａｒ^DA6およびＡｒ^DA7が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるＴ^DAは、同一でも異なっていてもよい。］

[Where:
^{m DA1, m DA2, m DA3} , m DA4, m DA5, m DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent. A plurality of ^GDAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. The plurality of ^TDAs may be the same or different. ]

In formula (DA) and formula (D-B), plurality of at least one of T ^DA is an aryl group with an alkyl group or 4 or more carbon atoms a cycloalkyl group having 4 or more carbon atoms as a substituent , or is preferably a monovalent heterocyclic group having as a substituent an alkyl group or 4 or more carbon atoms a cycloalkyl group having 4 or more carbon atoms, all of a plurality of T ^DA is 4 carbon atoms A monovalent group having the above alkyl group or an aryl group having a cycloalkyl group having 4 or more carbon atoms as a substituent, or an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms as a substituent. It is more preferably a heterocyclic group.

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1. m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are preferably the same integer.

G ^DA is preferably a group represented by the formula (GDA-11) ~ (GDA -15), these groups may have a substituent.

［式中、
＊は、式(D-A)におけるＡｒ^DA1、式(D-B)におけるＡｒ^DA1、式(D-B)におけるＡｒ^DA2、または、式(D-B)におけるＡｒ^DA3との結合を表す。
＊＊は、式(D-A)におけるＡｒ^DA2、式(D-B)におけるＡｒ^DA2、式(D-B)におけるＡｒ^DA4、または、式(D-B)におけるＡｒ^DA6との結合を表す。
＊＊＊は、式(D-A)におけるＡｒ^DA3、式(D-B)におけるＡ
³、式(D-B)におけるＡｒ^DA5、または、式(D-B)におけるＡｒ^DA7との結合を表す。
Ｒ^DAは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は更に置換基を有していてもよい。Ｒ^DAが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
* Is, Ar ^DA1 in the formula (DA), Ar ^DA1 in the formula (DB), Ar in formula (DB) ^DA2, or represents a bond between Ar ^DA3 in the formula (DB).
** is, Ar ^DA2 in the formula (DA), Ar ^DA2 in the formula (DB), or Ar ^DA4, in the formula (DB), represents a bond between Ar ^DA6 in the formula (DB).
*** is Ar ^DA3 in formula (DA), A in formula (DB)
³ represents a bond with Ar ^DA5 in the formula (DB) or Ar ^DA7 in the formula (DB).
R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may further have a substituent. When there are a plurality of ^RDA , they may be the same or different. ]

R ^DA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups have a substituent. May be.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably groups represented by the formulas (ArDA-1) to (ArDA-3).

［式中、
Ｒ^DAは前記と同じ意味を表す。
Ｒ^DBは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^DBが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
R ^DA represents the same meaning as described above.
R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RDBs , they may be the same or different. ]

R ^DB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, and still more preferably an aryl group.

T ^DA is preferably a group represented by the formula (TDA-1) ~ (TDA -3).

［式中、Ｒ^DAおよびＲ^DBは前記と同じ意味を表す。］

[Wherein, R ^DA and R ^DB represent the same meaning as described above. ]

In the groups represented by formulas (TDA-1) to (TDA-3), at least one of a plurality of R ^DA and R ^DB is an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms. It is preferable that at least one of the plurality of R ^DA is an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms, and all of the plurality of R ^DA have 4 carbon atoms. More preferably, the alkyl group is a cycloalkyl group having 4 or more carbon atoms.

  The group represented by the formula (D-A) is preferably a group represented by the formulas (D-A1) to (D-A3).

［式中、
Ｒ^p1、Ｒ^p2およびＲ^p3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基またはハロゲン原子を表す。Ｒ^p1およびＲ^p2が複数ある場合、それらはそれぞれ同一であっても異なっていてもよい。
ｎｐ１は、０〜５の整数を表し、ｎｐ２は０〜３の整数を表し、ｎｐ３は０または１を表す。複数あるｎｐ１は、同一でも異なっていてもよい。］

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^p1 and R ^p2 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]

  The group represented by the formula (D-B) is preferably a group represented by the formulas (D-B1) to (D-B3).

［式中、
Ｒ^p1、Ｒ^p2およびＲ^p3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基またはハロゲン原子を表す。Ｒ^p1およびＲ^p2が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
ｎｐ１は０〜５の整数を表し、ｎｐ２は０〜３の整数を表し、ｎｐ３は０または１を表す。ｎｐ１およびｎｐ２が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。］

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^p1 and R ^p2 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. When there are a plurality of np1 and np2, they may be the same or different. ]

  np1 is preferably 0 or 1, more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.

R ^p1 , R ^p2 and R ^p3 are preferably an alkyl group or a cycloalkyl group.

In formula (D-A1) to formula (D-A3) and formula (D-B1) to formula (D-B3), at least one of a plurality of R ^p1 is an alkyl group having 4 or more carbon atoms or a carbon atom A cycloalkyl group having a number of 4 or more is preferable, and all of the plurality of R ^p1 are preferably an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms.

  Examples of the group represented by the formula (DA) include groups represented by the formula (DA-1) to the formula (DA-17). In addition, examples of the group represented by the formula (D-B) include groups represented by the formula (D-B-1) to the formula (D-B-7).

R ^p represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, and these groups may have a substituent, such as a methyl group, a tert-butyl group, an n-hexyl group, A 2-ethylhexyl group, a group represented by the formula (Rp-1) or a 2-ethylhexyloxy group is preferred, and a tert-butyl group or a group represented by the formula (Rp-1) is more preferred.

<Metal complex>
Next, the metal complex of the present invention will be described. The metal complex of the present invention is represented by the formula (1).

Coordination metal complex represented by the formula (1) is as defined and iridium atom, and a ligand which is defined the number of index n _1, that number subscript in shape (3-n ₁₎ It is composed of a scale.

In formula (1), n ₁ is preferably 2 or 3, and more preferably 3.

In the formula (1), examples of the anionic bidentate ligand represented by A ¹ -G ¹ -A ² include the ligands represented by the following.

［式中、＊は、イリジウム原子と結合する部位を示す。］

[In formula, * shows the site | part couple | bonded with an iridium atom. ]

In the formula (1), the anionic bidentate ligand represented by A ¹ -G ¹ -A ² may be a ligand represented by the following. However, the anionic bidentate ligand represented by A ¹ -G ¹ -A ² is different from the ligand whose number is defined by the subscript n ₁ .

［式中、
＊は、イリジウム原子と結合する部位を表す。
Ｒ^L1は、水素原子、アルキル基、シクロアルキル基、アリール基、１価の複素環基またはハロゲン原子を表し、これらの基は置換基を有していてもよい。複数存在するＲ^L1は、同一でも異なっていてもよい。
Ｒ^L2は、アルキル基、シクロアルキル基、アリール基、１価の複素環基またはハロゲン原子を表し、これらの基は置換基を有していてもよい。］

[Where:
* Represents a site bonded to an iridium atom.
R ^L1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, or a halogen atom, and these groups optionally have a substituent. A plurality of R ^L1 may be the same or different.
R ^L2 represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent. ]

In the formula (1), R ^{1 to} R ⁶ and R ^{8 to} R ¹⁰ are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, because the metal complex of the present invention has excellent solubility in a solvent and film formability. An aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, still more preferably a hydrogen atom. Here, at least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (DA) or (DB), and preferably R ⁴ At least one selected from the group consisting of R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (DA).

It is preferable that at least one selected from the group consisting of R ⁴ and R ⁹ is a group represented by the formula (DA) or (DB), and R ⁴ represents the formula (DA) or (D -B) and R ⁹ is a hydrogen atom, or R ⁹ is a group represented by the formula (DA) or (DB) and R ⁴ is a hydrogen atom. It is more preferable.

In formula (1), R ⁷ and R ¹¹ are preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group, because the emission color of the metal complex of the present invention is pure blue.

In formula (1), preferably, in formula (1), R ⁹ is a group represented by formula (DA), a group represented by formula (DB), an aryl group, or a monovalent complex. It is preferably a cyclic group, more preferably a group represented by the formula (DA), a group represented by the formula (DB), or an aryl group, represented by the formula (DA). And a group represented by the formula (D-B) or a phenyl group is even more preferable. The aryl group represented by R ⁹ (may be a phenyl group) and a monovalent heterocyclic group may have a substituent, and the substituent is preferably an alkyl group or a cycloalkyl group.

  Examples of the metal complex represented by the formula (1) include metal complexes represented by the following formulas (Ir-1)-(Ir-22), and a light-emitting device obtained using the metal complex of the present invention Are preferable, and the metal complexes represented by the formulas (Ir-1) to (Ir-8) and the formulas (Ir-20) to (Ir-22) are preferable. Ir-1) to (Ir-8).

［式中、
Ｒ^L1およびＲ^L2は、前記と同様の意味を表す。
Ｒ^Lは、水素原子、または、炭素原子数４以下のアルキル基もしくは炭素原子数４以下のシクロアルキル基を表す。複数存在するＲ^Lは、同一でも異なっていてもよい。
Ｚ¹は、前記式（Ｄ−Ａ）または（Ｄ−Ｂ）で表される基である。Ｚ¹が複数存在する場合、それらは同一でも異なっていてもよい。］

[Where:
R ^L1 and R ^L2 represent the same meaning as described above.
R ^L represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a cycloalkyl group having 4 or less carbon atoms. A plurality of R ^L may be the same or different.
Z ¹ is a group represented by the above formula (DA) or (DB). When a plurality of Z ¹ are present, they may be the same or different. ]

In formulas (Ir-1) to (Ir-22), R ^L is preferably a group represented by any one of groups II of formulas (II-01) to (II-06).

  <Group II>

In the formulas (Ir-1) to (Ir-22), R ^L is preferably a group represented by the formula (II-01) or (II-02).

Z ¹ is preferably a group represented by the formula (DA).

Z ¹ is preferably a group represented by formula (D-A-1) to formula (D-A-18) or formula (D-B-1) to formula (D-B-7), More preferably, they are groups represented by formula (DA-1) to formula (DA-18).

  Examples of the metal complex represented by the formula (1) include metal complexes represented by the following formulas (Ir-26)-(Ir-35).

  In the light emitting device of the present invention, the metal complex of the present invention may be used alone or in combination of two or more.

  The metal complex represented by the formula (1) may have a plurality of geometric isomers, and any geometric isomer may be used. However, the luminance lifetime of the light-emitting element obtained using the metal complex of the present invention is high. Since it is excellent, the facial isomer is preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 99 mol%, particularly preferably at least 100 mol%, based on the entire metal complex of the present invention. %.

<Method for producing metal complex>
・ Production method 1
The metal complex of the present invention can be produced, for example, by a method of reacting a compound serving as a ligand with a metal compound. You may perform the functional group conversion reaction of the ligand of a metal complex as needed.

The compound represented by Formula (1) is represented by, for example, Step A in which a compound represented by Formula (M-1) is reacted with an iridium compound or a hydrate thereof, and Formula (M-2). And a step B of reacting the compound represented by the formula (M-1) with the ligand precursor represented by A ¹ -G ¹ -A ^2. Can do.

［式中、Ｒ^１〜Ｒ^１１およびｎ_２は、前記と同じ意味を表す。］

[Wherein, R ^{1 to} R ¹¹ and n ₂ represent the same meaning as described above. ]

  In Step A, examples of the iridium compound include iridium chloride and chloro (cyclooctadiene) iridium (I) dimer. Examples of the hydrate of the iridium compound include iridium chloride trihydrate.

  Step A and Step B are usually performed in a solvent. Solvents include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol and 2-ethoxyethanol; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether and diglyme Halogen compounds such as methylene chloride and chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene and mesitylene; N, N-dimethylformamide and N, N-dimethylacetamide Amide solvents such as acetone, dimethyl sulfoxide, water and the like.

  In Step A and Step B, the reaction time is usually 30 minutes to 150 hours, and the reaction temperature is usually between the melting point and boiling point of the solvent present in the reaction system.

  In step A, the amount of the compound represented by the formula (M-1) is usually 2 to 20 moles with respect to 1 mole of the iridium compound or hydrate thereof.

In step B, the amount of the compound represented by the formula (M-1) or the precursor of the ligand represented by A ¹ -G ¹ -A ² is the metal complex represented by the formula (M-2). It is 1-100 mol normally with respect to 1 mol.

  In step B, the reaction is preferably performed in the presence of a silver compound such as silver trifluoromethanesulfonate. When using a silver compound, the quantity is 2-20 mol normally with respect to 1 mol of metal complexes represented by a formula (M-2).

  The compound represented by the formula (M-1) is obtained by, for example, converting a compound represented by the formula (M-3) and a compound represented by the formula (2) into a Suzuki reaction, a Kumada reaction, a Stille reaction, and the like. It can be synthesized by a coupling reaction step.

［式中、
ｎ_２およびＺ¹は、前記と同じ意味を表す。
Ｒ^１２、Ｒ^１３、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１およびＲ^２２は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基、ハロゲン原子、−Ｂ(ＯＲ^W1)₂で表される基、アルキルスルホニルオキシ基、シクロアルキルスルホニルオキシ基またはアリールスルホニルオキシ基を表し、これらの基は置換基を有していてもよい。ただし、Ｒ^1５、Ｒ^1９、Ｒ^２０およびＲ^２１の少なくとも１つは、−Ｂ(ＯＲ^W1)₂で表される基、アルキルスルホニルオキシ基、シクロアルキルスルホニルオキシ基、アリールスルホニルオキシ基、塩素原子、臭素原子またはヨウ素原子である。
Ｗ¹は、−Ｂ(ＯＲ^W1)₂で表される基、アルキルスルホニルオキシ基、シクロアルキルスルホニルオキシ基、アリールスルホニルオキシ基、塩素原子、臭素原子またはヨウ素原子を表し、これらの基は置換基を有していてもよい。
Ｒ^W1は、水素原子、アルキル基、シクロアルキル基、アリール基またはアミノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^W1は、同一でも異なっていてもよく、互いに結合して、それぞれが結合する酸素原子とともに環構造を形成していてもよい。］

[Where:
n ₂ and Z ¹ represent the same meaning as described above.
R ¹² , R ¹³ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group , Alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, halogen atom, group represented by -B (OR ^W1 ) ₂ , alkylsulfonyloxy group, cycloalkylsulfonyloxy group or aryl A sulfonyloxy group is represented, and these groups may have a substituent. However, at least one of R ¹⁵ , R ¹⁹ , R ²⁰ and R ²¹ is a group represented by —B (OR ^W1 ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom , Bromine atom or iodine atom.
W ¹ represents a group represented by —B (OR ^W1 ) ₂ , an alkylsulfonyloxy group, a cycloalkylsulfonyloxy group, an arylsulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom, and these groups are a substituent. You may have.
R ^W1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an amino group, and these groups may have a substituent. A plurality of R ^W1 may be the same or different, and may be bonded to each other to form a ring structure together with the oxygen atom to which each is bonded. ]

Examples of the group represented by -B (OR ^W1 ) ₂ include groups represented by the following formulas (W-1)-(W-10).

Examples of the alkylsulfonyloxy group represented by W ¹ include a methanesulfonyloxy group, an ethanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.
Examples of the arylsulfonyloxy group represented by W ¹ include a p-toluenesulfonyloxy group.

W ¹ is preferably represented by -B (OR ^W1 ) ₂ because the coupling reaction of the compound represented by formula (2) and the compound represented by formula (M-3) proceeds easily. A trifluoromethanesulfonyloxy group, a bromine atom or an iodine atom, more preferably a group represented by the formula (W-7).

The alkylsulfonyloxy group, cycloalkylsulfonyloxy group and arylsulfonyloxy group represented by R ¹⁵ , R ¹⁹ , R ²⁰ and R ²¹ are the alkylsulfonyloxy group and cycloalkylsulfonyloxy group represented by W ¹ , respectively. And the same meaning as the arylsulfonyloxy group.

R ¹⁵ , R ¹⁹ , R ²⁰ and R ²¹ are preferably a bromine atom, an iodine atom or a group represented by the formula (W-7).

  This reaction is usually performed in a solvent. The solvent, reaction time, and reaction temperature are the same as those described for step A and step B.

  In this reaction, the amount of the compound represented by the formula (2) is usually 0.05 to 20 mol with respect to 1 mol of the compound represented by the formula (M-3).

  The compound represented by the formula (2) is, for example, described in documents such as International Publication No. 02/066733, Japanese Patent Application Laid-Open No. 2003-231692, International Publication No. 2003/079736, International Publication No. 2006/097717, and the like. It can be synthesized according to the method.

  The compound represented by the formula (M-3) can be synthesized, for example, according to the document of WO 06/121811.

・ Production method 2
The metal complex of the present invention can also be produced, for example, by a method in which a precursor of a metal complex and a precursor of a ligand of the metal complex are reacted.

  The compound represented by the formula (1) can be produced, for example, by subjecting a compound represented by the formula (2) and a metal complex represented by the formula (3) to a coupling reaction. This coupling reaction is the same as that described for the compound represented by formula (M-1).

［式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、ｎ₁、ｎ_２、Ａ¹、Ｇ¹およびＡ²は、前記と同じ意味を表す。］

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , n ₁ , n ₂ , A ¹ , G ¹ and A ² represents the same meaning as described above. ]

  The metal complex represented by the formula (3a) or (3b), which is one embodiment of the metal complex represented by the formula (3), is synthesized from, for example, the metal complex represented by the formula (4). Can do.

［式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、ｎ₁、ｎ_２、Ａ¹、Ｇ¹およびＡ²は、前記と同じ意味を表す。］

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , n ₁ , n ₂ , A ¹ , G ¹ and A ² are Represents the same meaning as above. ]

  More specifically, the metal complex represented by the formula (3a) can be synthesized by, for example, the step C of reacting the metal complex represented by the formula (4) with N-bromosuccinimide in an organic solvent. it can.

  In Step C, the amount of N-bromosuccinimide is usually 1 to 50 mol with respect to 1 mol of the compound represented by formula (4).

  More specifically, the metal complex represented by the formula (3b) is synthesized by, for example, the step D of reacting the metal complex represented by the formula (3a) with bis (pinacolato) diboron in an organic solvent. Can do.

  In the step D, the amount of bis (pinacolato) diboron is usually 1 to 50 mol with respect to 1 mol of the compound represented by the formula (3a).

  Step C and Step D are usually performed in a solvent. The solvent, reaction time, and reaction temperature are the same as those described for step A and step B.

［式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２１、Ｒ^２２、ｎ₁、ｎ_２、Ａ¹、Ｇ¹およびＡ²は、前記と同じ意味を表す。］ The metal complex represented by the formula (3c) or (3d), which is one embodiment of the metal complex represented by the formula (3), can be synthesized from, for example, a compound represented by the formula (5). it can.

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²¹ , R ²² , n ₁ , n ₂ , A ¹ , G ¹ and A ² are Represents the same meaning as above. ]

  More specifically, the metal complex represented by the formula (3c) can be synthesized by, for example, the step E in which the compound represented by the formula (5) is reacted with the iridium compound in an organic solvent. Step E can be performed by the same reaction as in step A and step B of production method 1.

  More specifically, the metal complex represented by the formula (3d) can be synthesized by, for example, the step F in which the compound represented by the formula (3c) is reacted with bis (pinacolato) diboron in an organic solvent. it can.

  In Step F, the amount of bis (pinacolato) diboron is usually 1 to 50 mol with respect to 1 mol of the compound represented by the formula (3c).

  Step E and Step F are usually performed in a solvent. The solvent, reaction time, and reaction temperature are the same as those described for step A and step B.

・ Production method 3
In the compound represented by the formula (1), when n ₁ is 3, for example, the compound represented by the formula (M-1) can be synthesized by a method including the step G of reacting the iridium compound. .

［式中、Ｒ^１〜Ｒ^１１およびｎ_２は、前記と同じ意味を表す。］

[Wherein, R ^{1 to} R ¹¹ and n ₂ represent the same meaning as described above. ]

  In Step G, examples of the iridium compound include tris (acetylacetonato) iridium (III) and iridium acetate (III).

  Step G is usually performed in a solvent, but may not be performed in a solvent. As the solvent, among those described for the step A and the step B, a solvent having a boiling point of 100 to 300 ° C. is preferable.

In Step G, the reaction time is usually 30 minutes to 150 hours.
In Step G, the reaction temperature is usually between the melting point and the boiling point of the solvent present in the reaction system, but is preferably 100 to 300 ° C, more preferably 200 to 300 ° C.

  In Step G, the compound represented by the formula (M-1) is usually 2 to 20 moles relative to 1 mole of the iridium compound.

-Common explanation of the manufacturing method 1 and the manufacturing method 2 In a coupling reaction, in order to accelerate | stimulate reaction, you may use catalysts, such as a palladium catalyst. Palladium catalysts include palladium acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) , Tris (dibenzylideneacetone) dipalladium (0) and the like.

  The palladium catalyst may be used in combination with a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, 1,1′-bis (diphenylphosphino) ferrocene. .

  When a palladium catalyst is used in the coupling reaction, the amount is usually an effective amount with respect to 1 mol of the compound represented by formula (2), formula (3), or formula (M-3), for example. Preferably, it is 0.00001-10 mol in terms of palladium element.

  In the coupling reaction, a base is used in combination as necessary.

  The compound, catalyst and solvent used in each reaction described in <Method for producing metal complex> may be used alone or in combination of two or more.

<Composition>
The composition of the present invention is selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material (different from the metal complex of the present invention), an antioxidant and a solvent. It contains at least one material and the metal complex of the present invention.

  In the composition of the present invention, the metal complex of the present invention may be contained singly or in combination of two or more.

[Host material]
The metal complex of the present invention is a composition with a host material having at least one function selected from the group consisting of hole injecting property, hole transporting property, electron injecting property, and electron transporting property. The light emitting element obtained using the metal complex has particularly excellent external quantum efficiency. In the composition of the present invention, the host material may be contained singly or in combination of two or more.

  In the composition containing the metal complex of the present invention and the host material, the content of the metal complex of the present invention is usually 0.05 to 80 when the total of the metal complex of the present invention and the host material is 100 parts by weight. Parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight.

Since the lowest excited triplet state (T ₁ ) of the host material is excellent in external quantum efficiency of a light-emitting device obtained using the composition of the present invention, the energy level is equivalent to T ₁ of the metal complex of the present invention. Or a higher energy level.

  As a host material, a light-emitting element obtained using the composition of the present invention can be produced by a solution coating process, and therefore, the host material is soluble in a solvent capable of dissolving the metal complex of the present invention. Is preferred.

  Host materials are classified into low molecular compounds and high molecular compounds.

  The low molecular weight compound (hereinafter referred to as “low molecular weight host”) preferable as the host material will be described.

[Low molecular host]
The low molecular host is preferably a compound represented by the formula (H-1).

［式中、
Ａｒ^Ｈ１およびＡｒ^Ｈ２は、それぞれ独立に、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。
ｎ^Ｈ１およびｎ^Ｈ２は、それぞれ独立に、０または１を表す。ｎ^Ｈ１が複数存在する場合、それらは同一でも異なっていてもよい。複数存在するｎ^Ｈ２は、同一でも異なっていてもよい。
ｎ^Ｈ３は、０以上の整数を表す。
Ｌ^Ｈ１は、アリーレン基、２価の複素環基、または、−［Ｃ（Ｒ^Ｈ１１）_２］ｎ^Ｈ１１−で表される基を表し、これらの基は置換基を有していてもよい。Ｌ^Ｈ１が複数存在する場合、それらは同一でも異なっていてもよい。
ｎ^Ｈ１１は、１以上１０以下の整数を表す。Ｒ^Ｈ１１は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Ｈ１１は、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。
Ｌ^Ｈ２は、−Ｎ（−Ｌ^Ｈ２１−Ｒ^Ｈ２１）−で表される基を表す。Ｌ^Ｈ２が複数存在する場合、それらは同一でも異なっていてもよい。
Ｌ^Ｈ２１は、単結合、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^Ｈ２１は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Where:
Ar ^H1 and Ar ^H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
n ^H1 and n ^H2 each independently represent 0 or 1. When a plurality of n ^H1 are present, they may be the same or different. A plurality of n ^H2 may be the same or different.
n ^H3 represents an integer of 0 or more.
L ^H1 represents an arylene group, a divalent heterocyclic group, or a group represented by — [C (R ^H11 ) ₂ ] n ^H11 —, and these groups optionally have a substituent. When a plurality of L ^H1 are present, they may be the same or different.
n ^H11 represents an integer of 1 or more and 10 or less. R ^H11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^H11 may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
L ^H2 represents a group represented by -N (-L ^H21 -R ^H21 )-. When a plurality of L ^H2 are present, they may be the same or different.
L ^H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. R ^H21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

Ar ^H1 and Ar ^H2 are phenyl group, fluorenyl group, spirobifluorenyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, thienyl group, benzothienyl group, dibenzothienyl group, furyl group, benzofuryl Group, dibenzofuryl group, pyrrolyl group, indolyl group, azaindolyl group, carbazolyl group, azacarbazolyl group, diazacarbazolyl group, phenoxazinyl group or phenothiazinyl group, phenyl group, spirobifluorenyl group, A pyridyl group, pyrimidinyl group, triazinyl group, dibenzothienyl group, dibenzofuryl group, carbazolyl group or azacarbazolyl group is more preferable, and a phenyl group, pyridyl group, carbazolyl group or azacarbazolyl group is preferred. Are more preferable, a group represented by the above formula (TDA-1) or (TDA-3) is particularly preferable, and a group represented by the above formula (TDA-3) is particularly preferable. This group may have a substituent.

As the substituent that Ar ^H1 and Ar ^H2 may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group is preferable, and an alkyl group, a cyclo An alkoxy group, an alkoxy group or a cycloalkoxy group is more preferable, an alkyl group or a cycloalkoxy group is more preferable, and these groups may further have a substituent.

n ^H1 is preferably 1. n ^H2 is preferably 0.

n ^H3 is generally an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1.

n ^H11 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and even more preferably 1.

R ^H11 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and a hydrogen atom or an alkyl group. It is more preferable that these groups may have a substituent.

L ^H1 is preferably an arylene group or a divalent heterocyclic group.

L ^H1 represents formulas (A-1) to (A-3), formulas (A-8) to (A-10), formulas (AA-1) to (AA-6), and formulas (AA-10) to It is preferably a group represented by (AA-21) or formulas (AA-24) to (AA-34), and is represented by formula (A-1), formula (A-2), formula (A-8), Group represented by Formula (A-9), Formula (AA-1) to (AA-4), Formula (AA-10) to (AA-15), or Formula (AA-29) to (AA-34) It is more preferable that Formula (A-1), Formula (A-2), Formula (A-8), Formula (A-9), Formula (AA-2), Formula (AA-4), Formula It is more preferable that it is group represented by (AA-10)-(AA-15), Formula (A-1), Formula (A-2), Formula (A-8), Formula (AA-2) , Formula (AA-4), Formula (AA-10), Formula (AA-12) or Formula A group represented by (AA-14) is particularly preferred, and is represented by formula (A-1), formula (A-2), formula (AA-2), formula (AA-4) or formula (AA-14). It is especially preferable that it is group represented by.

As the substituent that L ^H1 may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group, an aryl group A group or a monovalent heterocyclic group is more preferable, an alkyl group, an aryl group or a monovalent heterocyclic group is more preferable, and these groups may further have a substituent.

L ^H21 is preferably a single bond or an arylene group, more preferably a single bond, and this arylene group may have a substituent.

The definition and examples of the arylene group or divalent heterocyclic group represented by L ^H21 are the same as the definitions and examples of the arylene group or divalent heterocyclic group represented by L ^H1 .

R ^H21 is preferably an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.

Definitions and examples of the aryl group and monovalent heterocyclic group represented by R ^H21 are the same as those of the aryl group and monovalent heterocyclic group represented by Ar ^H1 and Ar ^H2 .

Definitions and examples of the substituent that R ^H21 may have are the same as the definitions and examples of the substituent that Ar ^H1 and Ar ^H2 may have.

  The compound represented by the formula (H-1) is preferably a compound represented by the formula (H-2).

［式中、Ａｒ^Ｈ１、Ａｒ^Ｈ２、ｎ^Ｈ３およびＬ^Ｈ１は、前記と同じ意味を表す。］

[Wherein, Ar ^H1 , Ar ^H2 , n ^H3 and L ^H1 represent the same meaning as described above. ]

  Examples of the compound represented by the formula (H-1) include compounds represented by the following formulas (H-101) to (H-118).

  Examples of the polymer compound used for the host material include a polymer compound that is a hole transport material described later and a polymer compound that is an electron transport material described later.

[Polymer host]
A polymer compound preferable as a host material (hereinafter referred to as “polymer host”) will be described.

  The polymer host is preferably a polymer compound containing a structural unit represented by the formula (Y).

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。］

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ]

The arylene group represented by Ar ^Y1 is more preferably the formula (A-1), the formula (A-2), the formula (A-6)-(A-10), the formula (A-19) or the formula (A A-20), more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19) These groups may have a substituent.

The divalent heterocyclic group represented by Ar ^Y1 is more preferably a formula (AA-1)-(AA-4), a formula (AA-10)-(AA-15), a formula (AA-18) -(AA-21), a group represented by formula (A-53) or formula (A-54), more preferably formula (AA-4), formula (AA-10), formula (AA- 12) a group represented by formula (AA-14) or formula (AA-33), and these groups may have a substituent.

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^Y1 and at least one divalent heterocyclic group are directly bonded, and further preferable. The ranges are the same as the more preferable ranges and further preferable ranges of the above-mentioned arylene group and divalent heterocyclic group represented by Ar ^Y1 .

  Examples of the “divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded” include groups represented by the following formulas, which have a substituent. You may do it.

［式中、Ｒ^XXは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein R ^XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^XX is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

The substituent that the group represented by Ar ^Y1 may have is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups may further have a substituent.

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-1)-(Y-10), and a composition of the polymer host and the metal complex of the present invention. Is a structural unit represented by the formula (Y-1)-(Y-3), preferably from the viewpoint of the luminance life of the light emitting device using, and from the viewpoint of electron transport properties, preferably the formula (Y- 4)-(Y-7), which is preferably a structural unit represented by the formula (Y-8)-(Y-10) from the viewpoint of hole transportability.

［式中、Ｒ^Y1は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよく、隣接するＲ^Y1同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. . A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

  The structural unit represented by the formula (Y-1) is preferably a structural unit represented by the formula (Y-1 ′).

［式中、Ｒ^Y11は、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよい。］

[Wherein, R ^Y11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^Y1 may be the same or different. ]

R ^Y11 is preferably an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｘ^Y1は、−Ｃ(Ｒ^Y2)₂−、−Ｃ(Ｒ^Y2)＝Ｃ(Ｒ^Y2)−またはＣ(Ｒ^Y2)₂−Ｃ(Ｒ^Y2)₂−で表される基を表す。Ｒ^Y2は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y2は、同一でも異なっていてもよく、Ｒ^Y2同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - or _{^{C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. You may do it.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ₂ — is preferably an alkyl group or a cycloalkyl group, both are aryl groups, and both are monovalent complex A cyclic group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group. May have a substituent. Two R ^{Y2 s} may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R ^Y2 forms a ring, the group represented by —C (R ^Y2 ) ₂ — Is preferably a group represented by the formula (Y-A1)-(Y-A5), more preferably a group represented by the formula (Y-A4), and these groups have a substituent. It may be.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ═C (R ^Y2 ) — is preferably both an alkyl group or a cycloalkyl group, or one of which is an alkyl group Alternatively, a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In X ^Y1 , four R ^Y2 in the group represented by —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — are preferably an alkyl group or a cycloalkyl group which may have a substituent. It is. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded. When R ^Y2 forms a ring, —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — The group represented is preferably a group represented by the formula (Y-B1)-(Y-B5), more preferably a group represented by the formula (Y-B3), and these groups are substituted. It may have a group.

［式中、Ｒ^Y2は前記と同じ意味を表す。］

[Wherein, R ^Y2 represents the same meaning as described above. ]

  The structural unit represented by the formula (Y-2) is preferably a structural unit represented by the formula (Y-2 ′).

［式中、Ｒ^Y1およびＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y1 and X ^Y1 represent the same meaning as described above. ]

［式中、Ｒ^Y1およびＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y1 and X ^Y1 represent the same meaning as described above. ]

  The structural unit represented by the formula (Y-3) is preferably a structural unit represented by the formula (Y-3 ′).

［式中、Ｒ^Y11およびＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y11 and X ^Y1 represent the same meaning as described above. ]

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｒ^Y3は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. R ^Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]

R ^Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

  The structural unit represented by the formula (Y-4) is preferably a structural unit represented by the formula (Y-4 ′), and the structural unit represented by the formula (Y-6) is represented by the formula (Y -6 ′) is preferred.

［式中、Ｒ^Y1およびＲ^Y3は前記と同じ意味を表す。］

[Wherein, R ^Y1 and R ^Y3 represent the same meaning as described above. ]

［式中、Ｒ^Y1は前記を同じ意味を表す。Ｒ^Y4は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. R ^Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

  As the structural unit represented by the formula (Y), for example, a structural unit comprising an arylene group represented by the formula (Y-101)-(Y-121), a formula (Y-201)-(Y-206) A structural unit consisting of a divalent heterocyclic group represented by the formula: at least one arylene group represented by the formula (Y-301)-(Y-304) and at least one divalent heterocyclic group: Examples thereof include a structural unit composed of a divalent group directly bonded.

The structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, is excellent in the luminance life of a light-emitting element using a composition of a polymer host and the metal complex of the present invention. Preferably it is 0.5-80 mol% with respect to the total amount of the structural unit contained in a high molecular compound, More preferably, it is 30-60 mol%.

A structural unit represented by formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group, or at least one arylene group and at least one divalent heterocyclic group directly bonded to each other. The structural unit that is a group is preferably the total amount of the structural units contained in the polymer compound because the charge transport property of the light-emitting device using the composition of the polymer host and the metal complex of the present invention is excellent. Is 0.5 to 30 mol%, more preferably 3 to 20 mol%.

  One type of structural unit represented by the formula (Y) may be contained in the polymer host, or two or more types may be contained.

  Since the polymer host is excellent in hole transport property, it is preferable that the polymer host further includes a structural unit represented by the following formula (X).

［式中、ａ^X1およびａ^X2は、それぞれ独立に、０以上の整数を表す。Ａｒ^X1およびＡｒ^X3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^X2およびＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。Ｒ^X1、Ｒ^X2およびＲ^X3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[ ^Wherein , a ^X1 and a ^X2 each independently represent an integer of 0 or more. Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent. R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

a ^X1 is preferably 2 or less, more preferably 1 because the luminance life of a light-emitting device using the composition of the polymer host and the metal complex of the present invention is excellent.

a ^X2 is preferably 2 or less, more preferably 0, because the luminance life of a light-emitting device using a composition of a polymer host and the metal complex of the present invention is excellent.

R ^X1 , R ^X2 and R ^X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. Also good.

The arylene group represented by Ar ^X1 and Ar ^X3 is more preferably a group represented by the formula (A-1) or the formula (A-9), more preferably a formula (A-1). These groups may have a substituent.

The divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 is more preferably represented by the formula (AA-1), the formula (AA-2) or the formula (AA-7)-(AA-26). These groups may have a substituent.

Ar ^X1 and Ar ^X3 are preferably an arylene group which may have a substituent.

As the arylene group represented by Ar ^X2 and Ar ^X4 , more preferably, the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9)-(A-11) Or it is group represented by a formula (A-19), and these groups may have a substituent.

The more preferable range of the divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 is the same as the more preferable range of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 .

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and the at least one divalent heterocyclic group are directly bonded to each other Further preferred ranges are the same as the more preferred ranges and further preferred ranges of the arylene group and divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 , respectively.

The divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and at least one divalent heterocyclic group are directly bonded to each other is at least represented by Ar ^Y1 in the formula (Y) Examples thereof include the same divalent groups in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.

Ar ^X2 and Ar ^X4 are preferably an arylene group which may have a substituent.

The substituents that the groups represented by Ar ^{X1 to} Ar ^X4 and R ^{X1 to} R ^X3 may have are preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups further have a substituent. You may do it.

  The structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1)-(X-7), more preferably the formula (X-1)-(X-6) And more preferably a structural unit represented by the formula (X-3)-(X-6).

［式中、Ｒ^X4およびＲ^X5は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、ハロゲン原子、１価の複素環基またはシアノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^X4は、同一でも異なっていてもよい。複数存在するＲ^X5は、同一でも異なっていてもよく、隣接するＲ^X5同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^X4 and R ^X5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or cyano. Represents a group, and these groups may have a substituent. A plurality of R ^X4 may be the same or different. A plurality of R ^X5 may be the same or different, and adjacent R ^X5 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

  Since the structural unit represented by the formula (X) has excellent hole transport properties, it is preferably 0.1 to 50 mol%, more preferably 1 to 50 mol% based on the total amount of the structural units contained in the polymer host. It is 40 mol%, More preferably, it is 5-30 mol%.

  Examples of the structural unit represented by the formula (X) include structural units represented by the formula (X1-1)-(X1-11), preferably the formula (X1-3)-(X1-10). ).

  In the polymer host, the structural unit represented by the formula (X) may be included alone or in combination of two or more.

  Examples of the polymer host include polymer compounds (P-1) to (P-6) shown in Table 1. Here, the “other” structural unit means a structural unit other than the structural unit represented by the formula (Y) and the structural unit represented by the formula (X).

  The polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be in other modes. A copolymer obtained by polymerization is preferred.

<Method for producing polymer host>
The polymer host can be produced by using a known polymerization method described in Chemical Review (Chem. Rev.), Vol. 109, pp. 897-1091 (2009), etc., and Suzuki reaction, Yamamoto reaction, Examples of the polymerization method include a coupling reaction using a transition metal catalyst such as a reaction, Stille reaction, Negishi reaction, and Kumada reaction.

  In the polymerization method, as a method of charging the monomer, a method of charging the entire amount of the monomer into the reaction system at once, a part of the monomer is charged and reacted, and then the remaining monomer is batched, Examples thereof include a method of charging continuously or divided, a method of charging monomer continuously or divided, and the like.

  Examples of the transition metal catalyst include a palladium catalyst and a nickel catalyst.

  Post-treatment of the polymerization reaction is a known method, for example, a method of removing water-soluble impurities by liquid separation, adding the reaction solution after polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying. These methods are performed alone or in combination. When the purity of the polymer host is low, it can be purified by a usual method such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  A composition containing a metal complex and a solvent of the present invention (hereinafter referred to as “ink”) is suitable for production of a light-emitting element using a printing method such as an inkjet printing method or a nozzle printing method.

  The viscosity of the ink may be adjusted according to the type of printing method, but when a solution such as an ink jet printing method is applied to a printing method that passes through a discharge device, clogging and flight bending at the time of discharge are less likely to occur. Preferably, it is 1 to 20 mPa · s at 25 ° C.

  The solvent contained in the ink is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink. Examples of the solvent include chlorine solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as THF, dioxane, anisole and 4-methylanisole; Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane, and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, and phenyl acetate Solvents: ethylene glycol, glycerin, 1,2-hex Examples include polyhydric alcohol solvents such as sundiol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. It is done. A solvent may be used individually by 1 type, or may use 2 or more types together.

  In the ink, the amount of the solvent is usually 1000 to 100,000 parts by weight, preferably 2000 to 20000 parts by weight with respect to 100 parts by weight of the metal complex of the present invention.

[Hole transport material]
The hole transport material is classified into a low molecular compound and a high molecular compound, preferably a high molecular compound, and more preferably a high molecular compound having a crosslinking group.

  Examples of the polymer compound include polyvinyl carbazole and derivatives thereof; polyarylene having an aromatic amine structure in the side chain or main chain and derivatives thereof. The polymer compound may be a compound to which an electron accepting site is bonded. Examples of the electron accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and fullerene is preferable.

  In the composition of the present invention, the compounding amount of the hole transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the metal complex of the present invention.

  A hole transport material may be used individually by 1 type, or may use 2 or more types together.

[Electron transport materials]
Electron transport materials are classified into low molecular compounds and high molecular compounds. The electron transport material may have a crosslinking group.

  Examples of low molecular weight compounds include metal complexes having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, and diphenoquinone. As well as these derivatives.

  Examples of the polymer compound include polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.

  In the composition of the present invention, the compounding amount of the electron transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the metal complex of the present invention.

  An electron transport material may be used individually by 1 type, or may use 2 or more types together.

[Hole injection material and electron injection material]
The hole injection material and the electron injection material are each classified into a low molecular compound and a high molecular compound. The hole injection material and the electron injection material may have a crosslinking group.

  Examples of the low molecular weight compound include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.

  Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain. A functional polymer.

  In the composition of the present invention, the compounding amounts of the hole injection material and the electron injection material are each usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the metal complex of the present invention. Part.

  Each of the hole injection material and the electron injection material may be used alone or in combination of two or more.

[Ion dope]
When the hole injection material or the electron injection material includes a conductive polymer, the electrical conductivity of the conductive polymer is preferably 1 × 10 ⁻⁵ S / cm to 1 × 10 ³ S / cm. In order to make the electric conductivity of the conductive polymer within such a range, the conductive polymer can be doped with an appropriate amount of ions.

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

  Doping ions may be used alone or in combination of two or more.

[Light emitting material]
Luminescent materials (different from the metal complex of the present invention) are classified into low molecular compounds and high molecular compounds. The light emitting material may have a crosslinking group.

  Examples of the low molecular weight compound include naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and triplet light-emitting complexes having iridium, platinum, or europium as a central metal.

  Examples of the polymer compound include phenylene group, naphthalenediyl group, anthracenediyl group, fluorenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, group represented by formula (X), carbazolediyl group, phenoxazine diyl And a polymer compound containing a group, a phenothiazinediyl group, an anthracenediyl group, a pyrenediyl group, and the like.

  The light emitting material preferably includes a triplet light emitting complex and a polymer compound.

  Examples of the triplet luminescent complex include the metal complexes shown below.

  In the composition of the present invention, the content of the light emitting material is usually 0.1 to 400 parts by weight with respect to 100 parts by weight of the metal complex of the present invention.

[Antioxidant]
The antioxidant may be any compound that is soluble in the same solvent as the metal complex of the present invention and does not inhibit light emission and charge transport. Examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  In the composition of the present invention, the compounding amount of the antioxidant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the metal complex of the present invention.

  Antioxidants may be used alone or in combination of two or more.

<Membrane>
The film contains the metal complex of the present invention.

  The film includes an insolubilized film obtained by insolubilizing the metal complex of the present invention in a solvent by crosslinking. The insolubilized film is a film obtained by crosslinking the metal complex of the present invention by an external stimulus such as heating or light irradiation. Since the insolubilized film is substantially insoluble in a solvent, the insolubilized film can be suitably used for stacking light emitting elements.

  The heating temperature for crosslinking the film is usually 25 to 300 ° C., and since the external quantum efficiency is excellent, it is preferably 50 to 250 ° C., more preferably 150 to 200 ° C.

  Types of light used for light irradiation for crosslinking the film are, for example, ultraviolet light, near ultraviolet light, and visible light.

  The film is suitable as a hole transport layer or a hole injection layer in the light emitting device.

  The film is made of ink, for example, spin coating method, 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 printing method. , Flexographic printing, offset printing, ink jet printing, capillary coating, and nozzle coating.

  The thickness of the film is usually 1 nm to 10 μm.

<Light emitting element>
The light-emitting device of the present invention is a light-emitting device obtained by using the metal complex of the present invention, and the metal complex of the present invention may be cross-linked intramolecularly or intermolecularly. It may be cross-linked within and between molecules.
As a structure of the light emitting element of this invention, it has an electrode which consists of an anode and a cathode, and a layer obtained using the metal complex of this invention provided between this electrode, for example.

[Layer structure]
The layer obtained using the metal complex of the present invention is usually one or more layers of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer, preferably a light emitting layer. is there. Each of these layers includes a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material. Each of these layers is the same as the above-described film production, in which a light-emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material are dissolved in the above-described solvent and ink is prepared and used. It can be formed using a method.

  The light emitting element has a light emitting layer between an anode and a cathode. The light-emitting element of the present invention preferably has at least one of a hole injection layer and a hole transport layer between the anode and the light-emitting layer from the viewpoint of hole injection and hole transport. From the viewpoint of injection property and electron transport property, it is preferable to have at least one of an electron injection layer and an electron transport layer between the cathode and the light emitting layer.

  As the material for the hole transport layer, electron transport layer, light emitting layer, hole injection layer and electron injection layer, in addition to the metal complex of the present invention, the above-described hole transport material, electron transport material, light emitting material, positive Examples thereof include a hole injection material and an electron injection material.

  The material of the hole transport layer, the material of the electron transport layer, and the material of the light emitting layer are used as solvents used in forming the layer adjacent to the hole transport layer, the electron transport layer, and the light emitting layer, respectively, in the production of the light emitting element. When dissolved, the material preferably has a cross-linking group in order to avoid dissolution of the material in the solvent. After forming each layer using a material having a crosslinking group, the layer can be insolubilized by crosslinking the crosslinking group.

  In the light emitting device of the present invention, as a method for forming each layer such as a light emitting layer, a hole transport layer, an electron transport layer, a hole injection layer, and an electron injection layer, when using a low molecular compound, for example, vacuum deposition from powder For example, a method using a film formation from a solution or a molten state may be used.

  The order, number and thickness of the layers to be laminated are adjusted in consideration of the external quantum efficiency and the luminance lifetime.

[Substrate / Electrode]
The substrate in the light-emitting element may be any substrate that can form electrodes and does not change chemically when the organic layer is formed. For example, the substrate is made of a material such as glass, plastic, or silicon. In the case of an opaque substrate, the electrode farthest from the substrate is preferably transparent or translucent.

  Examples of the material for the anode include conductive metal oxides and translucent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc. A conductive compound of silver, palladium and copper (APC); NESA, gold, platinum, silver and copper.

Examples of the material of the cathode include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, indium; two or more kinds of alloys thereof; Alloys of one or more species with one or more of silver, copper, manganese, titanium, cobalt, nickel, tungsten, tin; and graphite and graphite intercalation compounds. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
Each of the anode and the cathode may have a laminated structure of two or more layers.

[Usage]
In order to obtain planar light emission using the light emitting element, the planar anode and the cathode may be arranged so as to overlap each other. In order to obtain pattern-like light emission, a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, a layer that is desired to be a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There is a method, a method of forming an anode or a cathode, or both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display device capable of displaying numbers, characters, and the like can be obtained. In order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes and arranged orthogonally. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors, or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively, or can be driven active in combination with a TFT or the like. These display devices can be used for displays of computers, televisions, portable terminals and the like. The planar light emitting element can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source and display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  In the examples, the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Determined by The SEC measurement conditions are as follows.

[Measurement condition]
The polymer compound to be measured was dissolved in THF at a concentration of about 0.05% by weight, and 10 μL was injected into SEC. THF was used as the mobile phase of SEC and flowed at a flow rate of 2.0 mL / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

Liquid chromatograph mass spectrometry (LC-MS) was performed by the following method.
The measurement sample was dissolved in chloroform or THF to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). The LC-MS mobile phase was used while changing the ratio of acetonitrile and THF, and was allowed to flow at a flow rate of 0.2 mL / min. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size: 3 μm) was used.

NMR measurement was performed by the following method.
An NMR apparatus was prepared by dissolving 5 to 10 mg of a measurement sample in about 0.5 mL of deuterated chloroform (CDCl ₃ -d ₁ ), deuterated tetrahydrofuran (THF-d ₈ ) or deuterated acetone ((CD ₃ ) ₂ CO-d ₆ ). (Varian, Inc., trade name: MERCURY 300) or NMR apparatus (Bruker corporation, trade name: Avance III 600).

  High performance liquid chromatography (HPLC) area percentage values were used as indicators of compound purity. Unless otherwise specified, this value is a value at 254 nm by HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in THF or chloroform so that the concentration was 0.01 to 0.2% by weight, and 1 to 10 μL was injected into HPLC depending on the concentration. As the mobile phase of HPLC, acetonitrile and THF were used and allowed to flow at a flow rate of 1 mL / min in a gradient analysis of acetonitrile / THF = 100/0 to 0/100 (volume ratio). As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having equivalent performance was used. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

<Synthesis Example 1> Synthesis of Monomers CM1 to CM7 The structures of the monomers CM1 to CM7 used in the synthesis of the polymer compounds P1 and P2 are shown below.
Monomer CM1 was synthesized according to the method described in JP2011-174062.
Monomer CM2 was synthesized according to the method described in WO 2005/049546.
As the monomer CM3, a commercially available material was used.
Monomer CM4 was synthesized according to the method described in JP 2008-106241 A.
Monomer CM5 was synthesized according to the method described in JP 2010-189630 A.
Monomer CM6 and monomer CM7 were synthesized according to the method described in International Publication No. 2013/201188.

<Synthesis Example 2> Synthesis of Polymer Compound P1 Polymer compound P1 was synthesized according to the method described in JP 2012-144722 A using a monomer mixture P1a shown in Table 4 below. The Mn of the polymer compound P1 was 7.9 × 10 ⁴ , and the Mw was 3.4 × 10 ⁵ . The polymer compound P1 is a copolymer in which the structural units derived from the respective monomers are configured in the molar ratio shown in Table 4 below, according to the theoretical values obtained from the charged raw materials.

<Synthesis Example 3> Synthesis of Polymer Compound P2 (Step 1)
After making the inside of the reaction vessel an inert gas atmosphere, a monomer mixture P2a and toluene (84 mL) shown in Table 5 below were added and heated to 80 ° C. To this was added dichlorobis [tris (2-methoxyphenyl) phosphine] palladium (7.11 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (14.1 g), and then the mixture was heated to 100 ° C. under reflux. Stir for hours.

(Process 2)
Phenylboronic acid (98.5 mg), dichlorobis [tris (2-methoxyphenyl) phosphine] palladium (3.52 mg) and a 20 wt% aqueous tetraethylammonium hydroxide solution (14.1 g) were added to the resulting reaction solution. Then, it heated at 100 degreeC and stirred under reflux for 19 hours.

(Process 3)
A sodium diethyldithiacarbamate aqueous solution was added to the resulting reaction solution, and the mixture was stirred for 2 hours while being heated to 85 ° C. The resulting reaction solution was cooled to room temperature and the aqueous layer was removed, followed by washing twice with 3.6 wt% hydrochloric acid, twice with 2.5 wt% aqueous ammonia, and six times with ion-exchanged water. When the obtained solution was added dropwise to methanol, precipitation occurred. The obtained precipitate was collected by filtration and dried to obtain a solid. The obtained solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column through which toluene was passed in advance in order. When the obtained solution was added dropwise to methanol and stirred, precipitation occurred. The obtained precipitate was collected by filtration and dried to obtain polymer compound P2 (3.210 g). The Mn of the polymer compound P2 was 9.8 × 10 ⁴ , and the Mw was 2.7 × 10 ⁵ . The polymer compound P2 is a copolymer in which the structural units derived from the respective monomers are composed of the molar ratios shown in Table 5 below according to the theoretical values obtained from the raw materials.

  <Synthesis Example 4> Synthesis of Metal Complex MM1

  The metal complex MM1 was synthesized according to the methods described in International Publication No. 2006/121811, and Japanese Patent Application Laid-Open No. 2008-303150.

  <Example 1> Synthesis of metal complex MM2

  The reaction vessel was filled with an argon gas atmosphere, compound L2-a (5.75 g), pyridine (120 mL) and compound L2-b (13.5 g) were added, and the mixture was stirred at room temperature for 16 hours. The solution was concentrated under reduced pressure to give a white solid. The obtained white solid was added to water and then filtered under reduced pressure to obtain a solid. The obtained solid was purified by silica gel chromatography (dichloromethane) to obtain compound L2-c (14.4 g, yield 71%, white solid).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.06 (t, 1H), 7.83 (d, 1H), 7.69 (d, 1H), 7.38 (t, 1H ), 7.31 (m, 1H), 7.17-7.10 (m, 3H), 2.28 (m, 6H).

  After making the inside of reaction container argon gas atmosphere, compound L2-c (6.88g) and phosphorus pentachloride (4.64g) were added. Phosphoryl chloride (60 mL) was added dropwise thereto, and the mixture was stirred for 16 hours under heating and reflux. Then, it cooled to room temperature and concentrated the phosphoryl chloride under reduced pressure. Thereafter, 2-propanol (60 ml) and compound L2-d (48 mL) were added thereto and stirred for 16 hours. Thereafter, 12M hydrochloric acid was added dropwise thereto, and the mixture was stirred for 20 hours while heating under reflux. Then, it cooled to room temperature and filtered and remove | excluded the black solid. To the obtained filtrate, an aqueous sodium hydroxide solution was added to adjust the pH to about 12, and then toluene was added for extraction. The obtained organic layer was concentrated under reduced pressure to obtain a black oily substance. The resulting black oil was purified by silica gel chromatography (ethyl acetate / dichloromethane) to give compound L2-e (4.73 g, yield 64%, pale yellow powder). By repeating this work, the required amount of compound L2-e was obtained.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.69 (t, 1H), 7.36-7.25 (m, 3H), 7.17-7.14 (m, 3H) 7.03 (t, 1H), 6.93 (d, 1H), 1.96 (s.6H).

  After making the inside of the reaction vessel an argon gas atmosphere, compound L2-e (5.70 g), compound L2-f (16.3 g), triphenylphosphine (0.91 g), toluene (30 mL), ethanol (15 mL), 2M Aqueous sodium carbonate solution (30 mL) and bis (triphenylphosphine) palladium (II) dichloride (0.61 g) were added, and the mixture was stirred for 16 hours under heating to reflux. Then, it cooled to room temperature and added toluene and extracted. The obtained organic layer was washed with ion-exchanged water and then concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel chromatography (ethyl acetate / dichloromethane) to obtain Compound L2 (9.93 g, yield 99%).

¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO-d ₆ ) δ (ppm) = 7.82 (t, 1H), 7.79 (dt, 1H), 7.75 (m, 1H), 7 .70 (m, 4H), 7.60 (m, 4H), 7.52 (t, 1H), 7.50 (d, 2H), 7.46 (t, 1H), 7.30 (d, 1H), 7.28-7.20 (m, 3H), 7.18 (d, 1H), 2.00 (s, 6H), 1.39 (s, 18H).

  After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound L2 (1.5 g), iridium chloride hydrate (400 mg), 2-ethoxyethanol (36 mL) and water (18 mL) were added, and the mixture was stirred for 16 hours with heating under reflux. did. Then, it cooled to room temperature and concentrated the obtained reaction solution under reduced pressure. Thereafter, water (20 ml) was added thereto, the precipitated yellow-green solid was filtered, and the obtained solid was washed successively with water and methanol. The obtained solid was dried under reduced pressure to obtain Compound MM2-a (1.6 g, yellow-green powder).

  After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound MM2-a (1.6 g), silver trifluoromethanesulfonate (310 mg), dichloromethane (57 mL) and methanol (57 mL) were added, and the mixture was stirred for 4 hours with heating under reflux. . Then, it cooled to room temperature and concentrated the solvent under reduced pressure. Thereafter, sodium acetylacetonate (0.69 g) and acetonitrile (100 mL) were added thereto, and the mixture was stirred for 16 hours with heating under reflux. Then, it cooled to room temperature and concentrated the solvent under reduced pressure. Thereafter, dichloromethane (100 mL) was added thereto, followed by filtration. The obtained filtrate was concentrated under reduced pressure to obtain a brown solid. The obtained brown solid was purified by silica gel column chromatography (dichloromethane) to obtain Compound MM2 (0.94 g, yield 57%, yellow powder).

¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO-d ₆ ): δ (ppm) = 7.64-7.59 (m, 10H), 7.56-7.53 (m, 8H), 7 .47 (s, 6H), 7.42 (d, 2H), 7.35 (d, 4H), 7.33 (d, 2H), 7.04 (dd, 2H), 6.75 (d, 2H), 6.55 (d, 2H), 5.29 (s, 1H), 2.26 (s, 6H), 2.15 (s, 6H), 1.77 (s, 6H), 1. 37 (s, 36H).

  <Synthesis Example 5> Synthesis of metal complex MM3

金属錯体ＭＭ３は、国際公開第２００６／１２１８１１号および米国特許出願公開第２０１１／００５７５５９号明細書に記載の方法に準じて合成した。

The metal complex MM3 was synthesized according to the methods described in International Publication No. 2006/121811, and US Patent Application Publication No. 2011/0057559.

  <Example 2> Synthesis of metal complex MM4

  Compound L4-a was synthesized according to US Patent Application Publication No. 2011/0057559.

  After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound L4-a (9.9 g), Compound L4-b (15 g), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (0.11 g), Tris (Dibenzylideneacetone) dipalladium (0.12 g), 20 wt% tetraethylammonium aqueous solution (20 mL), toluene (200 mL) and ethanol (50 mL) were added, and the mixture was stirred for 18 hours under heating to reflux. Then, it cooled to room temperature and added toluene and extracted. The obtained organic layer was washed with ion-exchanged water, and then concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel chromatography (ethyl acetate / hexane), recrystallized using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure to give compound L4 (17 g, yield 90%). Got.

  After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound L4 (10 g), iridium chloride hydrate (2.2 g), 2-ethoxyethanol (120 mL) and water (40 mL) were added, and the mixture was stirred for 14 hours while heating under reflux. did. Then, when it cooled to room temperature and methanol was added, precipitation occurred. The obtained precipitate was filtered, and the obtained solid was washed with methanol and then dried under reduced pressure to obtain compound MM4-a (10 g, yellow powder).

  The reaction vessel was filled with an argon gas atmosphere, and then compound MM4-a (9.5 g), silver trifluoromethanesulfonate (31 g), dichloromethane (100 mL) and methanol (30 mL) were added, and the mixture was stirred overnight at room temperature. After the deposited precipitate was filtered, the obtained filtrate was concentrated under reduced pressure. Thereafter, compound L4 (7.8 g), 2,6-lutidine (6.7 mL) and diethylene glycol dimethyl ether (180 mL) were added thereto, and the mixture was stirred overnight under heating to reflux. Then, it cooled to room temperature, the mixed solvent of ion-exchange water and methanol was added, and the depositing deposit was filtered. The obtained solid was purified by silica gel chromatography (dichloromethane / hexane), recrystallized using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure to obtain metal complex MM4 (1.2 g, yield 6). .5%).

¹ H-NMR (600 MHz, (CD ₃ ) ₂ CO-d ₆ ) δ (ppm) = 8.01-7.97 (m, 9H), 7.91 (d, 6H), 7.81 (d, 12H), 7.59 (d, 12H), 7.25 (s, 3H), 6.92-6.89 (m, 6H), 6.57 (t, 3H), 5.87-5.81 (M, 6H), 2.89-2.86 (m, 3H), 2.52-2.48 (m, 3H), 1.87 (s, 12H), 1.42 (s, 36H), 1.38 (d, 9H), 1.16 (d, 9H), 1.12 (d, 9H), 1.07 (d, 9H), 0.80 (54H).

  Example 3 Synthesis of Compound MM5

  The metal complex MM5 was synthesized according to the synthesis of the metal complex MM4 except that the compound L-5a was used instead of the compound L-4b in the synthesis of the metal complex MM4.

¹ H-NMR (600 MHz, THF-d ₈ ): δ (ppm) = 7.88-7.87 (m, 6H), 7.84 (s, 3H), 7.75-7.72 (m, 6H), 7.69 (d, 12H), 7.52 (d, 12H), 7.06-7.05 (m, 3H), 6.86-6.85 (m, 3H), 6.82 (D, 3H), 6.52-6.50 (m, 3H), 6.37-6.36 (m, 6H), 2.89-2.85 (m, 3H), 2.51-2 .47 (m, 3H), 1.49 (s, 54H), 1.32 (d, 9H), 1.12 (d, 9H), 1.08 (d, 9H), 0.99 (d, 9H).

<Comparative Example CD1> Fabrication and Evaluation of Light-Emitting Element CD1 (Formation of Anode and Hole Injection Layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering. AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, was formed on the anode at a thickness of 35 nm by a spin coating method, and 170 ° C. on a hot plate in an air atmosphere. The hole injection layer was formed by heating for 15 minutes.

(Formation of hole transport layer)
Polymer compound P1 was dissolved in xylene at a concentration of 0.7% by weight. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated at 180 ° C. for 60 minutes on a hot plate in a nitrogen gas atmosphere. A transport layer was formed.

(Formation of light emitting layer)
Polymer compound P2 and metal complex MM1 (polymer compound P2 / metal complex MM1 = 60 wt% / 40 wt%) were dissolved in xylene at a concentration of 1.8 wt%. Using the obtained xylene solution, a film having a thickness of 75 nm was formed on the hole transport layer by a spin coating method, and a light emitting layer was formed by heating at 130 ° C. for 10 minutes in a nitrogen gas atmosphere. .

(Formation of cathode)
The substrate on which the light emitting layer is formed is depressurized to 1.0 × 10 ⁻⁴ Pa or less in a vapor deposition machine, and then, as a cathode, sodium fluoride is about 4 nm on the light emitting layer, and then on the sodium fluoride layer. Aluminum was deposited at about 80 nm. After vapor deposition, the light emitting element CD1 was produced by sealing using a glass substrate.

(Evaluation of light emitting element)
EL light emission was observed by applying a voltage to the light emitting device CD1. Table 6 shows drive voltage [V], emission spectrum peak wavelength [nm], and CIE chromaticity coordinates (x, y) at 100 cd / m ² , respectively.

<Example D1> Production and Evaluation of Light-Emitting Element D1 A light-emitting element D1 was produced in the same manner as Comparative Example CD1, except that metal complex MM2 was used instead of metal complex MM1 in Comparative Example CD1.
EL light emission was observed by applying a voltage to the light emitting element D1. Table 6 shows drive voltage [V], emission spectrum peak wavelength [nm], and CIE chromaticity coordinates (x, y) at 100 cd / m ² , respectively.

<Comparative Example CD2> Production and Evaluation of Light-Emitting Element CD2 In Comparative Example CD1, 1.8% by weight of polymer compound P2 and metal complex MM1 (polymer compound P2 / metal complex MM1 = 60% by weight / 40% by weight) Instead of the xylene solution dissolved at a concentration, the low-molecular compound SM1 (manufactured by Luminescence Technology, LT-N4013) and the metal complex MM3 (low-molecular compound SM1 / metal complex MM3 = 75% by weight / 25% by weight) are added. A light emitting device CD2 was produced in the same manner as in Comparative Example CD1, except that a toluene solution dissolved at a concentration of 0% by weight was used.
EL light emission was observed by applying a voltage to the light emitting device CD2. Table 7 shows drive voltage [V], emission spectrum peak wavelength [nm], and CIE chromaticity coordinates (x, y) at 100 cd / m ² .

<Example D2> Production and Evaluation of Light-Emitting Element D2 Light-emitting element D2 was produced in the same manner as Comparative Example CD2, except that metal complex MM4 was used instead of metal complex MM3 in Comparative Example CD2.
EL light emission was observed by applying a voltage to the light emitting element D2. Table 7 shows drive voltage [V], emission spectrum peak wavelength [nm], and CIE chromaticity coordinates (x, y) at 100 cd / m ² .

  From these results, it can be seen that the light-emitting element using the metal complex of the present invention is superior in driving voltage as compared with the light-emitting element using the metal complex MM1 or MM3.

Claims (11)

A metal complex represented by the following formula (1).

[Where:
n ₁ represents ₁ , 2 or 3. n ₂ represents 0 or 1. When a plurality of n ₂ are present, they may be the same or different.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group. Represents a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent. When a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are present, they may be the same or different. R ¹ and R ² , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ¹⁰ and R ¹¹ are bonded to each other and bonded to each other. And may form a ring. At least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the following formula (DA) or (DB).
A ¹ -G ¹ -A ² represents an anionic bidentate ligand, and G ¹ represents an atomic group constituting a bidentate ligand together with A ¹ and A ² . A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. When a plurality of A ¹ -G ¹ -A ² are present, they may be the same or different. ]

[Where:
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDA may be the same or different. ]

[Where:
^{m DA1, m DA2, m DA3} , m DA4, m DA5, m DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent. A plurality of ^GDAs may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDA may be the same or different. ] At least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (DA);
TDA in the formula ( ^DA ) is an aryl group having an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms as a substituent, or an alkyl group or carbon having 4 or more carbon atoms. The metal complex according to claim 1, which is a monovalent heterocyclic group having a cycloalkyl group having 4 or more atoms as a substituent. At least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (D-B);
Formula (D-B) in T ^DA is an aryl group or an alkyl group or carbon number of 4 or more carbon atoms, with an alkyl group or 4 or more carbon atoms a cycloalkyl group having 4 or more carbon atoms as a substituent The metal complex according to claim 1, which is a monovalent heterocyclic group having a cycloalkyl group having 4 or more atoms as a substituent. The metal complex according to claim 1, wherein at least one selected from the group consisting of R ⁴ and R ⁹ is a group represented by the formula (DA). The group represented by the formula (D-A) is a group represented by the following formula (D-A1), (D-A2) or (D-A3), The metal complex according to any one of the above.

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group or a halogen atom. When a plurality of R ^p1 and R ^p2 are present, they may be the same or different.
np1 represents an integer of 1 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]   The metal complex according to claim 5, wherein the group represented by the formula (DA) is a group represented by the formula (D-A1). The metal complex according to claim 1, wherein n ₂ is 1. Wherein n ₁ is 3, a metal complex according to any one of claims 1 to 7. The metal complex according to any one of claims 1 to 8,
The composition containing the high molecular compound containing the structural unit represented by a following formula (Y).

[In the formula (Y), Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded. And these groups may have a substituent. ] The metal complex according to any one of claims 1 to 8,
A composition comprising a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and at least one material selected from the group consisting of a solvent.   The light emitting element obtained using the metal complex as described in any one of Claims 1-8.