JP6543902B2 - Metal complex and light emitting device using the same - Google Patents

Description

  The present invention relates to a metal complex and a light emitting device using the metal complex.

  As a light-emitting material used for a light-emitting layer of a light-emitting element, various kinds of phosphorescent compounds which emit light from a triplet excited state have been studied. As such a phosphorescent compound, many metal complexes in which the central metal is a transition metal belonging to the fifth period or the sixth period have been studied.

  As a metal complex used for a light emitting layer of a light emitting element, Patent Document 1 proposes a metal complex 1 having a phenylisoquinoline structure having a dendron composed of three benzene rings as a ligand. Patent Document 2 proposes a metal complex 2 having a phenylpyridine structure having a dendron composed of a triazine ring and two benzene rings as a ligand. Further, in Patent Document 3, a metal complex having as a ligand a phenylpyridine structure having a dendron composed of a triazine ring and two benzene rings and a phenylisoquinoline structure having a dendron composed of three benzene rings Three have been proposed.

Unexamined-Japanese-Patent No. 2006-188673 JP, 2008-179617, A JP, 2011-105701, A

  However, the quantum yield (hereinafter, also referred to as “PLQY”) of the metal complex described in Patent Documents 1, 2 and 3 above is not necessarily sufficient. Since the quantum yield of the metal complex tends to decrease as the emission spectrum of the metal complex becomes longer, improvement in the quantum yield has been required for metal complexes exhibiting red phosphorescence.

  Then, this invention is a metal complex which shows red phosphorescence emission, Comprising: It aims at providing the metal complex which is excellent in a quantum yield. 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. Another object of the present invention is to provide a compound useful for the production of the metal complex.

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

［式中、
Ｍは、イリジウム原子または白金原子を表す。
ｍは１、２または３を表し、ｎは０、１または２を表す。Ｍがイリジウム原子の場合、ｍ＋ｎは３であり、Ｍが白金原子の場合、ｍ＋ｎは２である。
Ｚ^１、Ｚ^２およびＺ^３は、それぞれ独立に、−ＣＲ^Ｚ＝または窒素原子を表す。Ｒ^Ｚ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、アリールオキシ基、１価の複素環基、置換アミノ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^Ｚ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。Ｚ^１、Ｚ^２およびＺ^３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。但し、Ｚ^１、Ｚ^２およびＺ^３からなる群から選ばれる少なくとも１つは窒素原子である。
Ａｒ^１およびＡｒ^２は、それぞれ独立に、２つ以上の環が縮合した芳香族炭化水素基、または、２つ以上の環が縮合した複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^１およびＡｒ^２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^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６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、置換アミノ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^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６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^１１とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、Ｒ^１４とＲ^１５、および、Ｒ^１５とＲ^１６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。
Ａ^１−Ｇ^１−Ａ^２は、アニオン性の２座配位子を表す。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。Ｇ^１は、単結合、または、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−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。］

[In the formula,
M represents an iridium atom or a platinum atom.
m represents 1, 2 or 3; n represents 0, 1 or 2; When M is an iridium atom, m + n is 3, and when M is a platinum atom, m + n is 2.
Z ^{1, Z 2} and ^{Z 3} each independently represent a -CR ^Z = or a nitrogen atom. R ^Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, and these groups are substituents May be included. When two or more R ^Z exist, they may be the same or different. When ^two or more Z ¹ , Z ² and Z ³ exist, they may be the same or different. However, at least one selected from the group consisting of Z ¹ , Z ² and Z ³ is a nitrogen atom.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group in which two or more rings are fused, or a heterocyclic group in which two or more rings are fused, and these groups have a substituent It may be When a plurality of Ar ¹ and Ar ² exist, they may be the same or different.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent group Represents a heterocyclic group, a substituted amino group or a halogen atom, and these groups may have a substituent. When a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are present, they may be the same or different. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ respectively combine to form a ring with the carbon atom to which each is attached May be
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. Each of A ¹ and A ² independently represents a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. G ¹ represents a single bond or an atomic group constituting a bidentate ligand with A ¹ and A ² . When ^two or more A ¹ -G ¹ -A ² are present, they may be the same or different. ]

  The present invention secondly, at least one selected from the group consisting of the above metal complex, a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant and a solvent Provided is a composition containing the material.

  The present invention thirdly provides a light emitting device obtained by using the above metal complex.

  Fourth, the present invention provides a compound represented by the following formula (1M).

［式中、
Ｚ^１、Ｚ^２およびＺ^３は、それぞれ独立に、−ＣＲ^Ｚ＝または窒素原子を表す。Ｒ^Ｚ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、アリールオキシ基、１価の複素環基、置換アミノ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^Ｚ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。但し、Ｚ^１、Ｚ^２およびＺ^３からなる群から選ばれる少なくとも１つは窒素原子である。
Ａｒ^１およびＡｒ^２は、それぞれ独立に、２つ以上の環が縮合した芳香族炭化水素基、または、２つ以上の環が縮合した複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６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、置換アミノ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^１１とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、Ｒ^１４とＲ^１５、および、Ｒ^１５とＲ^１６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。］

[In the formula,
Z ^{1, Z 2} and ^{Z 3} each independently represent a -CR ^Z = or a nitrogen atom. R ^Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, and these groups are substituents May be included. When two or more R ^Z exist, they may be the same or different. However, at least one selected from the group consisting of Z ¹ , Z ² and Z ³ is a nitrogen atom.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group in which two or more rings are fused, or a heterocyclic group in which two or more rings are fused, and these groups have a substituent It may be
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, or a monovalent group Represents a heterocyclic group, a substituted amino group or a halogen atom, and these groups may have a substituent. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ respectively combine to form a ring with the carbon atom to which each is attached May be ]

  According to the present invention, it is possible to provide a metal complex that exhibits red phosphorescence and is excellent in quantum yield. Further, according to the present invention, a composition containing the metal complex and a light emitting device obtained using the metal complex can be provided. Furthermore, according to the present invention, a compound useful for the preparation of the metal complex can be provided. Since the metal complex of the present invention is excellent in quantum yield, a light emitting element obtained using the metal complex is excellent in external quantum efficiency.

It is a figure which shows the relationship between the largest peak wavelength of the emission spectrum of metal complex M3-M5 and metal complex CM1-CM3, and PLQY.

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

<Description of common terms>
Hereinafter, terms commonly used in the present 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.

  In the present specification, the hydrogen atom may be a deuterium atom or a light hydrogen atom.

  In the present specification, in structural formulas representing metal complexes, a solid line representing a bond with a 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 structural units contained in the polymer compound are 100 mol% in total.

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

  The end group of the polymer compound is preferably a stable group because the light emission characteristics and the luminance life may be reduced when the polymer compound is used for the preparation of a light emitting device if the polymerization active group remains as it is. It is. The terminal group is preferably a group conjugated with the main chain, and includes a group bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.

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

  The "constituent unit" means a unit which is present one or more in the polymer compound.

The "alkyl group" may be linear or branched. The carbon atom number of the linear alkyl group is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent. The carbon atom number of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent.
The carbon atom number of the "cycloalkyl group" is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the carbon atom number of the substituent.
The alkyl group and the cycloalkyl group may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoamyl group, 2 -Ethylbutyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3-propylheptyl, decyl, 3, 7-dimethyloctyl, 2-ethyloctyl, 2-hexyldecyl, dodecyl, Examples thereof include a cyclohexyl 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, an aryl group, a fluorine atom or the like. As the alkyl group, for example, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluoro Fluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5-di-hexylphenyl) propyl group, 6-ethyloxyhexyl group, cyclohexylmethyl group And cyclohexylethyl group.

The “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 the aryl group is usually 6 to 60, preferably 6 to 20, more preferably 6 to 10, not including the carbon atom number of the substituent.
The aryl group may have a substituent, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 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 atom 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 carbon atom number of the linear alkoxy group is usually 1 to 40, preferably 4 to 10, not including the carbon atom number of the substituent. The carbon atom number of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
The carbon atom number of the "cycloalkoxy group" is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
The alkoxy group and cycloalkoxy group may have a substituent, and examples thereof include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, Examples thereof include a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group.

The carbon atom number of the "aryloxy group" is usually 6 to 60, preferably 7 to 48, not including the carbon atom number of the substituent.
The aryloxy group may have a substituent, and examples thereof include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- The pyrenyloxy group and the group by which the hydrogen atom in these groups was substituted by the alkyl group, the cycloalkyl group, the alkoxy group, the cycloalkoxy group, the fluorine atom etc. are mentioned.

The “p-valent heterocyclic group” (p represents an integer of 1 or more) means p out of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting a ring from the heterocyclic compound. Means the remaining atomic groups excluding the hydrogen atom of Among the p-valent heterocyclic groups, carbon atoms constituting the ring or the remaining atomic groups obtained by removing p hydrogen atoms from hydrogen atoms directly bonded to a hetero atom from the aromatic heterocyclic compound "P-valent aromatic heterocyclic group" is preferred.
The “aromatic heterocyclic compound” is a complex such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole etc. Compounds in which the ring itself exhibits aromaticity, and heterocycles such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, benzopyran and the like themselves have aromatic rings fused to the aromatic ring even if they do not exhibit aromaticity It means a compound.

The carbon atom number of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the carbon atom number of the substituent.
The monovalent heterocyclic group may have a substituent, and examples thereof include thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and the like Groups in which a hydrogen atom in any of the groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like.

  The "halogen atom" represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

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

The "alkenyl group" may be linear or branched. The carbon atom number of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, not including the carbon atom number of the substituent. The carbon atom number of the branched alkenyl group is usually 3 to 30, preferably 4 to 20, not including the carbon atom number of the substituent.
The carbon atom number of the "cycloalkenyl group" is usually 3 to 30, preferably 4 to 20, not including the carbon atom number of the substituent.
The alkenyl group and cycloalkenyl group may have a substituent, and examples thereof include a vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4- The pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and the group which these groups have a substituent are mentioned.

The "alkynyl group" may be linear or branched. The carbon atom number of the alkynyl group is 2-20 normally, without including the carbon atom of a substituent, Preferably it is 3-20. The carbon atom number of a branched alkynyl group is 4-30 normally, without including the carbon atom of a substituent, Preferably it is 4-20.
The carbon atom number 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, and examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group A pentynyl group, 1-hexynyl group, 5-hexynyl group, and the group which these groups have a substituent are mentioned.

The "arylene group" means an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The carbon atom number of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, not including the carbon atom number of the substituent.
The arylene group may have a substituent, and examples thereof include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrendiyl group, dihydrophenanthrendiyl group, naphthacene diyl group, fluorenediyl group, pyrene diyl group, perylene diyl group, There may be mentioned a chrysendiyl group and a group in which these groups have a substituent, and preferably a group represented by the formula (A-1) to the formula (A-20). 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原子と共に環を形成していてもよい。］

[Wherein, R and R ^a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. Plural R and R ^a may be the same as or different from each other, and R ^a may be bonded to each other to form a ring with the atoms to which each is bonded. ]

The carbon atom number of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, and more preferably 4 to 15, not including the carbon atom number of the substituent.
The divalent heterocyclic group may have a substituent, and examples thereof include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, and the like. Preferred are dihydroacridines, furans, thiophenes, azoles, diazoles and triazoles, and divalent groups in which two hydrogen atoms of hydrogen atoms directly bonded to a carbon atom or hetero atom constituting a ring are removed, with preference given to Are groups represented by formulas (AA-1) to (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, the compounds of formulas (B-1) and (B-2) ), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8), (B-9), (B-10), It is a group represented by (B-11), (B-12), (B-13), (B-14), (B-15), (B-16) or (B-17).

［式中、これらの基は置換基を有していてもよい。］

[Wherein, these groups may have a substituent. ]

  The “substituent” is 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 , A cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substituent may be a crosslinking group.

  "Dendron" is a group having a regular tree-like branched structure (dendrimer structure) having an atom or ring as a branch point. In addition, as a compound (it may call it a dendrimer) which has a dendron as a partial structure, the structure as described in literature, such as WO02 / 067343, Unexamined-Japanese-Patent 2003-231692, WO2003 / 079736, WO2006 / 097717 etc., is mentioned, for example . The group represented by Formula (D-A) and the group represented by Formula (D-B) are also dendrons.

［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。］

[In the formula,
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
G ^DA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 exist, they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. The plurality of T ^DA 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。］

[In the formula,
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
G ^DA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. A plurality of G ^DA 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 a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are present, they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. The plurality of T ^DA may be the same or different. ]

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are usually integers of 10 or less, preferably 5 or less, more preferably 0 or 1, More preferably, it is 0. In addition, 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 formulas (GDA-11) to (GDA-15), and 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Ａｒ^DA3、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。］

[In the formula,
* 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 the formula (DA), Ar ^DA3 in the formula (DB), or Ar ^DA5, in the formula (DB), represents a bond between Ar ^DA7 in 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 ^RDAs , 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 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。］

[In the formula,
R ^DA has 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 multiple R ^DBs , 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, still more preferably an aryl group.

T ^DA is preferably a group represented by the formulas (TDA-1) to (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. ]

  The group represented by the formula (DA) is preferably a group represented by the formulas (DA1) to (DA3).

［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。］

[In the formula,
R ^p1 , R ^p2 and R ^p3 each independently represent 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. The 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。］

[In the formula,
R ^p1 , R ^p2 and R ^p3 each independently represent 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. np3 is preferably 0.

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

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

  In the formula (1), M is more preferably an iridium atom because the luminance life of the light emitting device using the metal complex of the present invention is excellent.

  In the formula (1), n is preferably 0 because the quantum yield of the metal complex of the present invention is more excellent and the synthesis of the metal complex of the present invention becomes easy.

  In the formula (1), when M is an iridium atom, m + n is 3, and m is preferably 2 or 3, and more preferably 3.

  In the formula (1), when M is a platinum atom, m + n is preferably 2, and m is preferably 2.

Wherein ^{(1), Z 1, Z} 2 and ^{Z 3} each independently represent a -CR ^Z = or a nitrogen atom. R ^Z is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, since it facilitates the synthesis of the metal complex of the present invention, and a hydrogen atom, an alkyl group or a cycloalkyl group is preferred. It is more preferably a group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In the formula (1), since the quantum yield of the metal complexes of the present invention is more excellent, it is preferable that at least two of the nitrogen atom selected from the group consisting of Z ^1, Z ² and Z ^3, Z ^1, Z ² And all of Z ³ are nitrogen atoms.

In the formula (1), Ar ¹ and Ar ² are preferably aromatic hydrocarbon groups in which two or more rings are condensed, because the quantum yield of the metal complex of the present invention is more excellent.

In the formula (1), Ar ¹ and Ar ² are preferably the same group because the synthesis of the metal complex of the present invention becomes easy.

  The aromatic hydrocarbon group in which two or more rings are fused means the remaining atom excluding one hydrogen atom directly bonded to a carbon atom constituting the ring from the aromatic hydrocarbon in which two or more rings are fused. Means a group. The carbon atom number of the aromatic hydrocarbon group in which two or more rings are fused is usually 8 to 60, preferably 8 to 20, more preferably 8 to 20, not including the carbon atom number of the substituent. 14 As a substituent which the aromatic hydrocarbon group which two or more rings condensed may have, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and an aryl group are mentioned.

  Examples of the aromatic hydrocarbon group in which two or more rings are condensed include groups represented by formulas (2-1) to (2-13), and the quantum yield of the metal complex of the present invention is more In order to be excellent, the group represented by the formula (2-1) to (2-5), (2-12) or (2-13) is preferable, and it is represented by the formula (2-1) or (2-2) Is more preferable, and a group represented by Formula (2-1) is more preferable.

［式中、Ｒ^２およびＲ^３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す。複数存在するＲ^２は、同一でも異なっていてもよく、隣接するＲ^２同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。複数存在するＲ^３は、同一でも異なっていてもよく、隣接するＲ^３同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。］

[Wherein, R ² and R ³ 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 monovalent heterocyclic group or a halogen atom . Plural R ^{2 s} may be the same or different, and adjacent R ^{2 s} may be bonded to each other to form a ring together with the atoms to which they are bonded. Plural R ^{3 s} may be the same or different, and adjacent R ^{3 s} may be bonded to each other to form a ring together with the atoms to which they are bonded. ]

  A heterocyclic group in which two or more rings are fused means a heterocyclic compound in which two or more rings are fused, excluding one hydrogen atom directly bonded to a carbon atom or a hetero atom constituting the ring. Means the remaining atomic groups. The carbon atom number of the heterocyclic group in which two or more rings are fused is usually 4 to 60, preferably 6 to 20, more preferably 8 to 14, not including the carbon atom number of the substituent. is there. As a substituent which the heterocyclic group which two or more rings condensed may have, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and an aryl group are mentioned.

  Examples of the heterocyclic group in which two or more rings are fused include groups represented by formulas (2-21) to (2-35), and the quantum yield of the metal complex of the present invention is more excellent. It is preferable that it is group represented by (2-21)-(2-28), and it is more preferable that it is group represented by (2-25)-(2-28).

［式中、Ｒ^２は前記と同じ意味を表す。Ｒ^４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、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す。］

[Wherein, R ² represents the same meaning as described above. R ⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom. ]

In formulas (2-1) to (2-13) and formulas (2-21) to (2-35), R ² is a hydrogen atom, an alkyl group, or the like because the synthesis of the metal complex of the present invention is facilitated. It is preferably a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and a hydrogen atom, an alkyl group or a cycloalkyl group Is more preferred.

In the formulas (2-1) to (2-13), R ³ facilitates the synthesis of the metal complex of the present invention, and therefore a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group Is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and more preferably a hydrogen atom, an alkyl group or an aryl group.

In formulas (2-21) to (2-35), R ⁴ facilitates the synthesis of the metal complex of the present invention, and therefore a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group Is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or an aryl group.

In the formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group because the synthesis of the metal complex of the present invention becomes easy. Preferably a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, a hydrogen atom, an alkyl group or an aryl group Is more preferred.

In the formula (1), at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is an aryl group because the quantum yield of the metal complex of the present invention is more excellent. It is preferably a monovalent heterocyclic group or a substituted amino group, more preferably an aryl group or a monovalent heterocyclic group, and still more preferably an aryl group. The aryl group, monovalent heterocyclic group and substituted amino group are preferably groups represented by formula (D-A) or (D-B).

In the formula (1), at least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group represented by the formula (D-A) or (D-B) In the case of formula (D-A1), (D-A2), (D-A3), (D-B1), (D-B2) or (D-B2), the synthesis of the metal complex of the present invention is facilitated. It is preferably a group represented by -B3), more preferably a group represented by the formula (D-A1) or the formula (D-B1), and further preferably a group represented by the formula (D-A1) preferable. The group represented by Formula (D-A1) is preferably a group represented by Formula (3-1). The group represented by Formula (D-B1) is preferably a group represented by Formula (3-2).

［式中、
Ｒ^３１、Ｒ^３２およびＲ^３３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、置換アミノ基またはハロゲン原子を表す。Ｒ^３１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く、複数存在するＲ^３２は、同一でも異なっていてもよく、複数存在するＲ^３３は、同一でも異なっていてもよい。］

[In the formula,
R ³¹ , R ³² and R ³³ 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 monovalent heterocyclic group, a substituted amino group or a halogen Represents an atom. When a plurality of R ³¹ are present, they may be the same or different, and a plurality of R ³² may be the same or different, and a plurality of R ³³ may be the same or different. ]

In formulas (3-1) and (3-2), since R ³¹ is more excellent in the quantum yield of the metal complex of the present invention, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic ring It is preferably a group or a substituted amino group, more preferably a hydrogen atom or an alkyl group.
In formulas (3-1) and (3-2), since R ³² is more excellent in the quantum yield of the metal complex of the present invention, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic ring It is preferably a group or a substituted amino group, and more preferably an alkyl group, a cycloalkyl group or an aryl group.
In formulas (3-1) and (3-2), R ³³ facilitates the synthesis of the metal complex of the present invention, and therefore a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group Is preferably a hydrogen atom or an alkyl group.

In formula (1), R ¹⁴ is preferably a group represented by formula (D-A) or formula (D-B), since the quantum yield of the metal complex of the present invention is more excellent, D-A1), (D-A2), (D-A3), (D-B1), (D-B2) or (D-B3) is more preferably a group represented by the formula (D-A) More preferably, it is a group represented by A1) or (D-B1). The group represented by Formula (D-A1) is preferably a group represented by Formula (3-1). The group represented by Formula (D-B1) is preferably a group represented by Formula (3-2).

In the formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ are preferably hydrogen atoms because the synthesis of the metal complex of the present invention is facilitated.

Examples of the anionic bidentate ligand represented by A ¹ -G ¹ -A ² in the formula (1) include the ligands represented by the following.

［式中、＊は、イリジウム原子または白金原子と結合する部位を示す。］

[Wherein, * represents a site binding to an iridium atom or a platinum atom. ]

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

［式中、
＊は、イリジウム原子または白金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。］

[In the formula,
* Represents a site to be bonded to an iridium atom or a platinum 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 may have a substituent. Plural 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 may have a substituent. ]

  Examples of the metal complex represented by the formula (1) include metal complexes represented by the formulas (Ir-1) to (Ir-20). Among these, metal complexes represented by the formulas (Ir-1) to (Ir-11) are preferable because the quantum yield of the metal complex of the present invention is more excellent, and the formulas (Ir-2) to (Ir-6) are preferable. The metal complex represented by (Ir-8) or (Ir-8) is more preferable. Further, among these, metal complexes represented by the formulas (Ir-2) to (Ir-6) are more preferable because the synthesis of the metal complex of the present invention becomes easy, and the formulas (Ir-2) and (Ir-2) are more preferable. Particularly preferred is a metal complex represented by -4) or (Ir-6).

［式（Ｉｒ−１）〜（Ｉｒ−２０）中、
Ｚ^１、Ｚ^２、Ｚ^３、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^２は、前記と同意味を表す。
Ｒ^Ｌ５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、置換アミノ基またはハロゲン原子を表す。Ｒ^Ｌ５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。］

[In the formulas (Ir-1) to (Ir-20),
Z ¹ , Z ² , Z ³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ² are as defined above.
R ^L5 represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a substituted amino group or a halogen atom. When two or more R ^L5 are present, they may be the same or different. ]

In formulas (Ir-1) to (Ir-20),
R ^L5 is a group represented by Formula (II-1) to Formula (II-14) of the following Group II and a group represented by Formula (III-1) to the Formula (III-17) of the following Group III It is preferable that it is a selected group.

  <Group II>

  <Group III>

  Specific examples of the metal complex represented by the formula (1) include metal complexes represented by the formulas (Ir-101) to (Ir-112).

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

  A plurality of geometric isomers can be considered for the metal complex represented by the formula (1), and any geometric isomer may be used, but the half bandwidth of the emission spectrum of the metal complex of the present invention is more excellent, The facial form is preferably 80% by mole or more, more preferably 90% by mole or more, still more preferably 99% by mole or more, and still more preferably 100% by mole (i.e., the other) with respect to the entire metal complex. Particular preference is given to the absence of geometric isomers.

<Compound>
Next, the compounds of the present invention will be described. The compound of the present invention is a compound represented by the formula (1M). The compounds of the present invention are compounds useful in the preparation of the metal complexes of the present invention described later.

Examples and preferred ranges of Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , Ar ¹¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 in} the formula (1M) are those of the formula (1) Examples and preferred ranges of Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as in the following.

  Examples of the compound represented by the formula (1M) include compounds represented by the formulas (1M-1) to (1M-20). Among these, compounds represented by the formulas (1M-1) to (1M-9) are preferable because the synthesis of the compound of the present invention is facilitated.

［式（１Ｍ−１）〜（１Ｍ−２０）中、Ｚ^１、Ｚ^２、Ｚ^３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^２、Ｒ^３およびＲ^４は、前記と同じ意味を表す。］

[In the formulas (1M-1) to (1M-20), Z ¹ , Z ² , Z ³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ² , R ³ and R ⁴ have the same meaning as described above. ]

  Specific examples of the compound represented by the formula (1M) include compounds represented by the formulas (1M-101) to (1M-112).

<Method for Producing Metal Complex Represented by Formula (1) and Compound Represented by Formula (1M)>
[Manufacturing method 1]
The metal complex represented by Formula (1) which is a metal complex of this invention can be manufactured, for example by the method of making the compound and the metal compound which become a ligand react. If necessary, functional group conversion reaction of the metal complex ligand may be performed.

Among the metal complexes represented by the formula (1), those in which M is an iridium atom are, for example,
Step A1 of synthesizing a metal complex represented by the formula (1M-1) by reacting a compound represented by the formula (1M) with an iridium compound or a hydrate thereof
Step B1 of reacting the metal complex represented by the formula (1M-1) with the compound represented by the formula (1M) or the precursor of the ligand represented by A ¹ -G ¹ -A ² It can be manufactured by a method.

［式（１Ｍ）および（１Ｍ−１）中、Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６は、前記と同じ意味を表す。］

[Wherein, in the formulas (1M) and (1M-1), Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are as defined above] Represents the meaning. ]

  In the step A1, examples of the iridium compound include iridium chloride, tris (acetylacetonato) iridium (III), chloro (cyclooctadiene) iridium (I) dimer, iridium acetate (III), and water of the iridium compound Examples of the solvate include iridium chloride trihydrate.

Step A1 and step B1 are usually performed in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol and 2-ethoxyethanol; and ether solvents such as diethyl ether , tetrahydrofuran, dioxane, cyclopentyl methyl ether and diglyme; Halogen solvents 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, N, N-dimethylacetamide and the like Amide solvents of the following: acetone, dimethyl sulfoxide, water

  In step A1 and step B1, the reaction time is usually 30 minutes to 150 hours, and the reaction temperature is usually between the melting point and the boiling point of the solvent present in the reaction system.

  In step A1, the amount of the compound represented by the formula (1M) is generally 2 to 20 mol, per 1 mol of the iridium compound or a hydrate thereof.

In step B1, the amount of the compound represented by the formula (1M) or the precursor of the ligand represented by A ¹ -G ¹ -A ² is 1 mole of the metal complex represented by the formula (1M-1) Is usually 1 to 100 moles.

  In step B1, the reaction is preferably carried out in the presence of a silver compound such as silver trifluoromethanesulfonate. When a silver compound is used, the amount is usually 2 to 20 mol, per 1 mol of the metal complex represented by the formula (1M-1).

  The compound represented by the formula (1M) includes, for example, a compound represented by the formula (1M-2) and a compound represented by the formula (1M-3), such as Suzuki reaction, Kumada reaction, Stille reaction, etc. It can synthesize | combine by the process C1 to make a coupling reaction.

［式（１Ｍ−２）および（１Ｍ−３）中、
Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６は、前記と同じ意味を表す。
Ｗ^１およびＷ^２は、それぞれ独立に、−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を形成していてもよい。］

[In the formulas (1M-2) and (1M-3),
Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meaning as described above.
W ¹ and W ² each independently represent 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 These groups may have a substituent. 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. The plurality of R ^{W1 s} may be the same or different, and may be bonded to each other to form a ring together with the oxygen atom to which each is bonded. ]

As group represented by -B (OR ^<W1> ) ₂ , group represented by following formula (W-1)-(W-10) is mentioned, for example.

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 p-toluenesulfonyloxy group.

As W ¹ , a coupling reaction between the compound represented by the formula (1M-2) and the compound represented by the formula (1M-3) easily proceeds, and therefore, it is represented by —B (OR ^W1 ) ₂ A trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom is preferred. Among these, a chlorine atom, a bromine atom or a group represented by the formula (W-7) is more preferable because the synthesis of the compound represented by the formula (1M-2) is easy.

As W ² , a group represented by —B (OR ^W1 ) ₂ , a trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom is preferable, and among these, a compound represented by the formula (1M-3) The group represented by a chlorine atom, a bromine atom or a formula (W-7) is more preferable because of easy synthesis of

  The coupling reaction (step C1) of the compound represented by the formula (1M-2) with the compound represented by the formula (1M-3) is usually performed in a solvent. The solvents used, the reaction time and the reaction temperature are the same as those described for step A1 and step B1.

  In the coupling reaction of the compound represented by the formula (1M-2) with the compound represented by the formula (1M-3), the amount of the compound represented by the formula (1M-3) is represented by the formula (1M-2) It is a 0.05-20 mol normally with respect to 1 mol of compounds represented.

  The compound represented by the formula (1M-2-1) which is one of the embodiments of the compound represented by the formula (1M-2) is, for example, a compound represented by the formula (1M-2-1a) It can manufacture by the process D1 which makes a coupling reaction with the compound represented by Formula (1M-2-1b). This coupling reaction is the same as that described for the compound represented by formula (1M).

［式中、
Ｒ^２は、前記と同じ意味を表す。
Ｗ^３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、前記と同じ意味を表す。］

[In the formula,
R ² represents the same meaning as described above.
W ³ 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 substituents May be included. R ^W1 represents the same meaning as described above. ]

  The compound represented by the formula (1M-3-1) which is one of the embodiments of the compound represented by the formula (1M-3) is, for example, a compound represented by the formula (1M-3-1a) It can manufacture by the process E1 which makes the coupling reaction with the compound represented by Formula (1M-3-1b). This coupling reaction is the same as that described for the compound represented by formula (1M).

［式中、
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６は、前記と同じ意味を表す。
Ｗ^４およびＷ^５は、それぞれ独立に、−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、前記と同じ意味を表す。］

[In the formula,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meaning as described above.
W ⁴ and W ⁵ each independently represent 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 These groups may have a substituent. R ^W1 represents the same meaning as described above. ]

[Manufacturing method 2]
The metal complex represented by the formula (1) which is the metal complex of the present invention can also be produced, for example, by a method of reacting a precursor of the metal complex with a precursor of a ligand of the metal complex.

Among the metal complexes represented by the formula (1), those in which M is an iridium atom are, for example,
It can manufacture by coupling-reacting the compound represented by Formula (1M-2), and the metal complex represented by Formula (1M-4). This coupling reaction is the same as that described for the compound represented by formula (1M).

［式（１Ｍ−４）および（１Ｍ−２）中、
ｍ、ｎ、Ｚ^１、Ｚ^２、Ｚ^３、Ａｒ^１、Ａｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＷ^１は、前記と同じ意味を表す。
Ｗ^６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、前記と同じ意味を表す。］

[In the formulas (1M-4) and (1M-2),
m, n, Z ¹ , Z ² , Z ³ , Ar ¹ , Ar ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and W ¹ have the same meaning as described above.
W ⁶ 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 substituents May be included. R ^W1 represents the same meaning as described above. ]

The compound represented by the formula (1M-4a) which is one of the embodiments of the compound represented by the formula (1M-4) is a compound represented by the formula (1M-4a-1) and an iridium compound or the compound thereof Step A2 of synthesizing a metal complex represented by the formula (1M-4a-2) by reacting with a hydrate, and
It can manufacture by the method including the process B2 which makes the metal complex represented by Formula (1M-4a-2), and the compound represented by Formula (1M-4a-1) react.

  The reactions in step A2 and step B2 are the same as the reactions described in step A1 and step B2, respectively.

[Coupling Reaction in Production Method 1 and Production Method 2]
In the coupling reaction, a catalyst such as a palladium catalyst may be used to promote the reaction. Examples of the palladium catalyst include, for example, palladium acetate, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium ( II), tris (dibenzylideneacetone) dipalladium (0).

  The palladium catalyst may be used in combination with phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, 1,1'-bis (diphenylphosphino) ferrocene and the like. .

  When a palladium catalyst is used in the coupling reaction, its amount is usually effective, for example, with respect to 1 mol of the compound represented by the formula (1M-2), the formula (1M-3) or the formula (1M-4) The amount is preferably 0.00001 to 10 moles in terms of palladium element.

  In the coupling reaction, if necessary, a base may be used in combination.

  The compound, catalyst and solvent used in each reaction described in <Method for producing metal complex> may be used singly 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 comprises the metal complex of the present invention as a composition with a host material having at least one function selected from hole injecting property, hole transporting property, electron injecting property and electron transporting property. The external quantum efficiency of the light-emitting element obtained by using it becomes more excellent. 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 a host material, the content of the metal complex of the present invention is usually 0. 0 when the total of the metal complex of the present invention and the host material is 100 parts by weight. It is 01 to 80 parts by weight, preferably 0.05 to 40 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 20 parts by weight.

The lowest excitation triplet state (T ₁ ) of the host material is the lowest excitation triplet state (T ₁ ) of the metal complex of the present invention because the external quantum efficiency of the light emitting device obtained using the composition of the present invention is more excellent. It is preferable that the energy level is equal to or higher than ₁ ).

  As a host material, from the viewpoint of producing a light emitting device obtained using the composition of the present invention by a solution coating process, it exhibits solubility in a solvent capable of dissolving the metal complex of the present invention Is preferred.

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

  As a low molecular weight compound used for a host material, for example, a compound having a carbazole structure, a compound having a triarylamine structure, a compound having a phenanthroline structure, a compound having a triaryltriazine structure, a compound having an azole structure, a benzothiophene structure And compounds having a benzofuran structure, compounds having a fluorene structure, and compounds having a spirofluorene structure. Specific examples of the low molecular weight compound used for the host material include the compounds shown below.

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

[Polymer host]
The polymer compound preferable as a host compound (hereinafter, also referred to as "polymer host") will be described.

  The polymer host is preferably a polymer compound containing a constitutional 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。］

[ ^Wherein , Ar ^{Y 1} represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one type of divalent heterocyclic group are directly bonded, Groups may have a substituent. ]

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

More preferably, the divalent heterocyclic group represented by Ar ^Y1 is represented by Formula (AA-1) to Formula (AA-4), Formula (AA-10) to Formula (AA-15), or Formula (AA-). 18) to a group represented by Formula (AA-21), Formula (AA-33) or Formula (AA-34), and more preferably Formula (AA-4), Formula (AA-10), Formula (AA) AA-12), a group represented by Formula (AA-14) or Formula (AA-33), and these groups may have a substituent.

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

  Examples of “a 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, and these groups have a substituent It may be done.

［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 may have a substituent. ]

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

The substituent which 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) to (Y-10), and a composition of a polymer host and the metal complex of the present invention Preferably, from the viewpoint of the luminance life of the light emitting device using the above, it is a structural unit represented by the formula (Y-1), (Y-2) or (Y-3), and from the viewpoint of the electron transportability, Preferably, they are structural units represented by formulas (Y-4) to (Y-7), and from the viewpoint of hole transportability, they are preferably represented by formulas (Y-8) to (Y-10) It is a structural unit.

［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 may have a substituent] . Plural 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 atoms to which they are bonded. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups may 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 represents a group represented by —C (R ^Y2 ) ₂ —, —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 atoms to which they are 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 May be

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

In X ^Y1 , the combination of two R ^{Y2 in} a 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. Or a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In ^{X Y1, -C (R Y2)} 2 -C (R Y2) 2 - 4 pieces of R ^Y2 in the group represented by is preferably an optionally substituted alkyl group or a cycloalkyl group 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 attached, and in the case where R ^Y2 forms a ring, -C (R ^Y2 ) ₂ -C (R ^Y2 ) _2- The group represented is preferably a group represented by formulas (Y-B1) to (Y-B5), more preferably a group represented by 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. ]

［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

［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 may 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, structural units consisting of arylene groups represented by the formulas (Y-101) to (Y-121), formulas (Y-201) to (Y-206) Wherein at least one arylene group represented by the formulas (Y-301) to (Y-304) and at least one bivalent heterocyclic group are The structural unit which consists of the bivalent group directly couple | bonded is mentioned.

The structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, is excellent in luminance life of a light emitting device using a composition of a polymer host and the metal complex of the present invention, Preferably it is 0.5-100 mol% with respect to the total amount of the structural unit contained in a high molecular compound, More preferably, it is 60-95 mol%.

A constituent unit represented by the formula (Y), wherein Ar ^{Y 1} is a divalent heterocyclic group, or a bivalent in which at least one arylene group and at least one divalent heterocyclic group are directly bonded. Since 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, the structural unit which is a group of is preferably relative to the total amount of the structural units contained in the polymer compound. Is 0.5 to 30 mol%, more preferably 3 to 20 mol%.

  The constituent unit represented by the formula (Y) may be contained alone in the polymer host, or two or more kinds may be contained.

  It is preferable that the polymer host further includes a structural unit represented by the following formula (X) because the polymer host is excellent in hole transportability.

［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。Ａｒ^X2およびＡｒ^X4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^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。Ｒ^X2およびＲ^X3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。］

[ ^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 may 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 These groups may have a substituent. When a plurality of Ar ^X2 and Ar ^X4 are present, they may be the same or different. Each of R ^X1 , R ^X2 and R ^X3 independently 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 a plurality of R ^X2 and R ^X3 exist, they may be the same or different. ]

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

a ^{X 2} is preferably 2 or less, more preferably 0, because the luminance lifetime of the light emitting device using the composition of the 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, these groups having a substituent It is also good.

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

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

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

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

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

More preferable range of arylene group and divalent heterocyclic group in a 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 And the more preferable ranges are respectively the same as the more preferable ranges and the more preferable ranges of the arylene group and the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 respectively.

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

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

The substituent which the group represented by Ar ^{X1 to} Ar ^X4 and R ^{X1 to} R ^X3 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups further have a substituent. It may be done.

  The structural unit represented by formula (X) is preferably a structural unit represented by formulas (X-1) to (X-7), and more preferably formulas (X-1) to (X-6) Or more preferably structural units represented by formulas (X-3) to (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 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, halogen atom, 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. Plural R ^{X5 s} may be the same or different, and adjacent R ^{X5 s} may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]

  The structural unit represented by the formula (X) is excellent in hole transportability, and 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 2 to 30 mol%.

  Examples of the structural unit represented by the formula (X) include structural units represented by the formulas (X1-1) to (X1-11), preferably a group represented by the formulas (X1-3) to (X1-10) It is a structural unit represented by).

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

  Examples of the polymer host include polymer compounds P-1 to P-7 in Table 1 below.

［表中、ｐ、ｑ、ｒ、ｓおよびｔは、各構成単位のモル比率を示す。ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝１００であり、かつ、１００≧ｐ＋ｑ＋ｒ＋ｓ≧７０である。その他の構成単位とは、式（Ｙ）で表される構成単位、式（Ｘ）で表される構成単位以外の構成単位を意味する。］

[In the table, p, q, r, s and t indicate the molar ratio of each constituent unit. p + q + r + s + t = 100, and 100 p p + q + r + s 70 70. The other structural unit means a structural unit other than the structural unit represented by Formula (Y) and the structural unit represented by Formula (X). ]

  The polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may have other embodiments, but from the above viewpoint, plural types of polymers may be used. It is preferable that it is a copolymer formed by copolymerizing a raw material monomer.

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

  In the above-mentioned polymerization method, as a method of charging the monomers, a method of charging the whole amount of the monomers at once into the reaction system, charging a part of the monomers and reacting them, then batching the remaining monomers, A method of charging continuously or by division, a method of charging monomers continuously or by division, etc. may be mentioned.

  Although it does not specifically limit as a transition metal catalyst, A palladium catalyst and a nickel catalyst are mentioned.

  Post-treatment of the polymerization reaction is carried out by a known method, for example, a method of removing water-soluble impurities by liquid separation, adding a reaction solution after the polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate and drying it. The method of making it etc. is 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 and the like.

  The composition containing the metal complex of the present invention and a solvent (hereinafter sometimes referred to as "ink") is suitable for producing a light emitting device 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 in the case where a solution such as an inkjet printing method is applied to a printing method via a discharge device, in order to prevent clogging at the discharge and flying deflection. And preferably 1 to 20 mPa · s at 25 ° C.

  The solvent contained in the ink is preferably a solvent capable of dissolving or uniformly dispersing the solid content in the ink. As the solvent, for example, chlorinated solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, etc .; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methylanisole; toluene, 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 cellsolve acetate, methyl benzoate and phenyl acetate System solvents; ethylene glycol, Polyhydric alcohol solvents such as serine and 1,2-hexanediol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like And amide solvents of the following. The solvents may be used alone or in combination of two or more.

  In the ink, the compounding amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20 000 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 weight compound and a high molecular weight compound, a high molecular weight compound is preferable, and a high molecular weight compound having a crosslinking group is more preferable.

  Examples of the polymer compound include polyvinylcarbazole and derivatives thereof; polyarylenes having an aromatic amine structure in the side chain or main chain and derivatives thereof. The macromolecular compound may be a compound having an electron accepting moiety bound thereto. Examples of the electron accepting moiety include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone and the like, with preference given to fullerene.

  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.

  The hole transport material may be used alone or in combination of two or more.

[Electron transport material]
Electron transport materials are classified into low molecular weight compounds and high molecular weight 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. And as well as their derivatives.

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

  In the composition of the present invention, the compounding amount of the electron transporting 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.

  The electron transporting material may be used alone or in combination of two or more.

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

  As a low molecular weight compound, metal phthalocyanines, such as copper phthalocyanine; Carbon; Metal oxides, such as molybdenum and tungsten; Metal fluorides, such as lithium fluoride, sodium fluoride, cesium fluoride, potassium fluoride, etc. are mentioned, for example.

  As the polymer compound, for example, polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, polythienylenevinylene, polyquinoline and polyquinoxaline, and derivatives thereof; containing a group represented by the formula (X) in the main chain or side chain Conducting polymers, such as a polymer, are mentioned.

  In the composition of the present invention, the compounding amount of the hole injecting material and the electron injecting material is generally 1 to 400 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight of the metal complex of the present invention. It is a department.

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

[Ion doping]
When the hole injecting material or the electron injecting material contains a conductive polymer, the conductivity of the conductive polymer is preferably 1 × 10 ⁻⁵ S / cm to 1 × 10 ³ S / cm. The conductive polymer can be doped with an appropriate amount of ions in order to bring the conductivity of the conductive polymer into such a range.

  The type of ion to be doped is an anion if it is a hole injecting material, and a cation if it is an electron injecting material. Examples of the anion include polystyrene sulfonate ion, alkyl benzene sulfonate ion and camphor sulfonate ion. Examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutyl ammonium ion.

  The ion to be doped may be one kind or two or more kinds.

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

  The low molecular weight compounds include, for example, naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, and a triplet light emitting complex having iridium, platinum or europium as a central metal.

  As the polymer compound, for example, phenylene group, naphthalenediyl group, fluorenedyl group, phenanthrendiyl group, dihydrophenanthrendiyl group, group represented by formula (X), carbazole diyl group, phenoxazine diyl group, phenothiazine diyl Examples thereof include polymer compounds containing a group, an anthracenediyl group, a pyrenediyl group and the like.

  The light emitting material may include low molecular weight compounds and high molecular weight compounds, and preferably includes triplet light emitting complexes and high molecular weight compounds.

  As a triplet light emission complex, the metal complex shown below is mentioned, for example.

  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 a compound which is soluble in the same solvent as the metal complex of the present invention and does not inhibit light emission and charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  In the composition of the present invention, the blending 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.

  The antioxidant may be used alone or in combination of two or more.

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

  The film also includes an insolubilized film in which the metal complex of the present invention is insolubilized by crosslinking to a solvent. 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 the solvent, it can be suitably used for laminating the light emitting element.

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

  The type of light used for light irradiation to crosslink the film is, for example, ultraviolet light, near ultraviolet light, and visible light.

  The film is suitable as a light emitting layer in a light emitting device.

  The film is formed using an ink, for example, spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method And flexo 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 intramolecularly or intermolecularly cross-linked, and the metal complex of the present invention is It may be crosslinked intramolecularly and intermolecularly.
The structure of the light emitting device of the present invention includes, for example, an electrode composed of an anode and a cathode, and a layer obtained using the metal complex of the present invention provided between the electrodes.

[Layer structure]
The layer obtained using the metal complex of the present invention is usually at least one layer of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer, preferably a light emitting layer is there. Each of these layers contains a light emitting material, a hole transporting material, a hole injecting material, an electron transporting material, and an electron injecting material. These layers are prepared by dissolving the light emitting material, the hole transporting material, the hole injecting material, the electron transporting material, and the electron injecting material in the above-mentioned solvent, preparing the ink, and using the same film as the above-mentioned film It can be formed using the method.

  The light emitting element has a light emitting layer between the anode and the cathode. The light emitting device of the present invention preferably has at least one of a hole injecting layer and a hole transporting layer between the anode and the light emitting layer, from the viewpoint of hole injecting property and hole transporting property, From the viewpoint of injectability and electron transportability, 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 materials of the hole transport layer, the electron transport layer, the light emitting layer, the hole injection layer and the electron injection layer, in addition to the metal complex of the present invention, the above-mentioned hole transport material, electron transport material, light emitting material, positive A hole injection material and an electron injection material can be mentioned.

  The material of the hole transport layer, the material of the electron transport layer and the material of the light emitting layer are respectively used as solvents used in forming the hole transport layer, the electron transport layer and the layer adjacent to the light emitting layer in the preparation of the light emitting device. When dissolving, it is preferable that the material has a crosslinking group in order to avoid dissolving the material in the solvent. After each layer is formed using a material having a crosslinking group, the layer can be insolubilized by crosslinking the crosslinking group.

  In the case of using a low molecular weight compound as a method of forming each layer such as a light emitting layer, a hole transport layer, an electron transport layer, a hole injection layer, an electron injection layer in the light emitting device of the present invention, vacuum evaporation from powder, for example The method includes film formation from a solution or a molten state, and when using a polymer compound, for example, film formation from a solution or a molten state.

  The order, number and thickness of layers to be stacked may be adjusted in consideration of the external quantum efficiency and the device life.

[Substrate / electrode]
The substrate in the light emitting element may be any substrate that can form an electrode and does not change chemically when forming an organic layer, and is, for example, a substrate made of a material such as glass, plastic, or silicon. In the case of an opaque substrate, it is preferred that the electrode furthest from the substrate be transparent or translucent.

  Examples of the material of the anode include conductive metal oxides and semitransparent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc. Conductive compounds; complexes of silver, palladium and copper (APC); NESA, gold, platinum, silver, copper.

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

[Use]
In order to obtain planar light emission using a light emitting element, a planar anode and a cathode may be arranged to overlap. In order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of a planar light-emitting element is used. 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 so that several electrodes can be turned ON / OFF independently, a segment type display device capable of displaying numbers, characters, etc. 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 orthogonal to each other. Partial color display and multi-color display can be performed by a method of separately applying a plurality of types of polymer compounds different in emission color and a method of 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 as displays of computers, televisions, portable terminals, and the like. A planar light emitting element can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar light source for illumination. If a flexible substrate is used, it can also be used as a curved light source and display device.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The measurement of LC-MS was performed by the following method.
The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technology, trade name: 1100 L CMSD). The mobile phase of LC-MS was used at a flow rate of 0.2 mL / min with varying ratios of acetonitrile and tetrahydrofuran. The column used was L-column 2 ODS (3 μm) (manufactured by Chemical Evaluation and Research Organization, inner diameter: 2.1 mm, length: 100 mm, particle diameter 3 μm).

The measurement of MALDI-TOF / MS was performed by the following method.
A sample solution was prepared by dissolving about 0.1 mg of a measurement sample in 200 μL of tetrahydrofuran. About 4 mg of 1,1,4,4-tetraphenyl-1,3-butadiene was dissolved in 400 μL of tetrahydrofuran to prepare a matrix solution. 10 microliters of sample solutions and 50 microliters of matrix solutions were mixed, this was apply | coated to the MALDI plate, and the measurement of MALDI-TOFMS was performed. The measurement was performed using a MALDI-TOF MS apparatus: REFLEX III (manufactured by Bruker) in a measurement mode: reflector mode, acceleration voltage: 27.5 kV, and laser: N ₂ (337 nm).

The measurement of NMR was performed by the following method.
5 to 10 mg of a measurement sample is dissolved in about 0.5 mL of heavy chloroform (CDCl ₃ ), heavy tetrahydrofuran (THF-d ₈ ) or methylene dichloride (CD ₂ Cl ₂ ), and an NMR apparatus (Varian, Inc. (Varian, Inc.) is used. (Trade name: MERCURY 300).

  The value of high performance liquid chromatography (HPLC) area percentage was used as an index of compound purity. This value is a value at 254 nm in high performance liquid chromatography (HPLC, manufactured by Shimadzu Corporation, trade name: LC-20A) unless otherwise specified. At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform so as to have a concentration of 0.01 to 0.2% by weight, and 1 to 10 μL was injected into HPLC depending on the concentration. The mobile phase of HPLC was flowed by using acetonitrile and tetrahydrofuran at a flow rate of 1 mL / min with gradient analysis of acetonitrile / tetrahydrofuran = 100/0 to 0/100 (volume ratio). As columns, Kaseisorb LC ODS 2000 (manufactured by Tokyo Kasei Kogyo Co., Ltd.) or an ODS column having equivalent performance was used. As a detector, a photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used.

The measurement of TLC-MS was performed by the following method.
The measurement sample is dissolved in toluene, tetrahydrofuran or chloroform at an arbitrary concentration, and applied on a TLC plate for DART (YSK5-100 manufactured by Techno Applications, Inc.) to make a TLC-MS (manufactured by JEOL Ltd.), a product It measured using the name JMS-T100TD (The AccuTOF TLC). The helium gas temperature at the time of measurement was adjusted in the range of 200 to 400 ° C.

The measurement of PLQY and emission spectrum was performed by the following method.
The metal complex was dissolved in xylene to a concentration of 0.0008% by weight. The obtained xylene solution was placed in a 1 cm square quartz cell, and oxygen was degassed by bubbling nitrogen gas to prepare a measurement sample. The PLQY and the emission spectrum of the obtained measurement sample were measured using an absolute PL quantum yield measurement apparatus (automatically controlled electric monochrome light source type) (C9920-02G, manufactured by Hamamatsu Photonics K. K.). The excitation wavelength was 400 nm.

  Example 1 Synthesis of Metal Complex M1

(Stage 1: Synthesis of Compound M1b)
The reaction vessel was changed to a nitrogen gas atmosphere, 1-bromonaphthalene (compound M1a, 132.5 g) and tetrahydrofuran (dehydrated product, 3.1 L) were added, and the mixture was cooled to -73 ° C while stirring. Then, the hexane solution (1.6 mol / L, 400 mL) of n-butyllithium was dripped there, stirring the reaction liquid in reaction container at -73 degreeC. The resulting reaction solution is referred to as "reaction solution A".
The inside of another reaction vessel was changed to a nitrogen gas atmosphere, then cyanuric chloride (59.0 g) and tetrahydrofuran (dehydrated product, 1.0 L) were added, and the mixture was cooled to -75.degree. C. with stirring. After that, the reaction solution A in the reaction vessel was added dropwise thereto with stirring at -75 ° C, and after completion of the dropwise addition, the temperature was raised to room temperature and stirred overnight at room temperature. After that, dilute aqueous ammonium chloride solution (500 mL) was added thereto, and the solvent was evaporated under reduced pressure. The obtained residue was dissolved in chloroform (1.5 L), and then sequentially washed with water (1 L) and 5% by weight brine (1 L). After that, it was dried using anhydrous sodium sulfate and concentrated until the amount of solvent became about half. Thereafter, n-hexane (400 mL) was added thereto, followed by filtration using silica gel, and then the obtained filtrate was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and acetonitrile and then crystallization using a mixed solvent of acetonitrile and n-hexane. Thereafter, the resultant was dried under reduced pressure at 50 ° C. overnight to obtain compound M1b (74.3 g, yield 63%) as a white solid. The HPLC area percentage value of compound M1b was 98.0%.

TLC / MS (DART positive): m / z ⁺ = 368 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.15 to 9.11 (mult, 2H), 8.55 (dd, 2H), 8.14 (d, 2H), 8 .00 (dd, 2H), 7.70-7.57 (mult, 6H).

(Stage 2: Synthesis of metal complex M1)
After making the inside of the reaction vessel shielded from light a nitrogen gas atmosphere, a compound M1b (61.4 g), a metal complex M0 (43.1 g) synthesized according to the method described in JP-A-2008-179617, cesium carbonate (81.5 g) Add bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (0.9 g), 1,4-dioxane (783 mL) and ion-exchanged water (5 mL), and add at 36 Stir for hours. The resulting reaction solution was filtered, and the obtained filtrate was evaporated under reduced pressure. The resulting residue is purified by silica gel column chromatography using a mixed solvent of toluene and chloroform, then crystallized using a mixed solvent of toluene and acetonitrile, and then crystallized using a mixed solvent of chloroform and acetonitrile And purified by Thereafter, the resultant was dried under reduced pressure at 50 ° C. overnight to obtain metal complex M1 (19 g, yield 27%) as a red solid. The HPLC area percentage value of the metal complex M1 was 99.0%.

LC / MS (APCI positive): m / z = 1649.5 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.01 (d, 3 H), 8.79 (d, 6 H), 8.61 (dd, 3 H), 8.10 (dd) , 6H), 8.00 (d, 3H), 7.85 (d, 3H), 7.77 (t, 12H), 7.49-7.36 (mult, 18H), 7.03-6. 90 (mult, 9H).

  Example 2 Synthesis of Metal Complex M2

  The inside of the reaction vessel shielded from light was changed to a nitrogen gas atmosphere, and then metal complex M1 (15.7 g), chloroform (460 mL) and N, N-dimethylformamide (DMF) (44 mL) were added. Then, it stirred, cooling to 0 degreeC using the ice bath. After that, N-bromosuccinimide (NBS) (6.76 g) was added thereto. Then, it stirred for 3 hours, cooling using an ice bath, and stirred at room temperature for 3 hours. Thereafter, chloroform (2 L) and dichloromethane (3 L) were added thereto, and the mixture was washed successively with 5 wt% aqueous sodium thiosulfate solution (720 mL) and ion-exchanged water (720 mL). The obtained organic layer was dried over anhydrous sodium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was dissolved in dichloromethane (2.5 L) and filtered through celite and silica gel, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified by crystallization using a mixed solvent of dichloromethane and methanol, and then dried to obtain metal complex M2 (17 g, yield 86%) as a white solid. The HPLC area percentage value of the metal complex M2 was 98.2%.

MALDI-TOF / MS (positive): m / z = 1882 [M] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 8.92 (d, 3 H), 8.76 (d, 6 H), 8.61 (dd, 3 H), 8.10 (dd) , 6H), 7.94-7.90 (mult, 6H), 7.78 (t, 12H), 7.50-7.36 (mult, 18H), 7.04 (dd, 3H), 6. 88 (d, 3H).

  Example 3 Synthesis of Metal Complex M3

  After making the inside of the reaction vessel shielded from light into an argon gas atmosphere, metal complex M2 (342 mg), compound M3a (277 mg) synthesized according to the method described in JP-A-2011-195829, tetrahydrofuran (20 mL), tetrakis (triphenylphosphine) Palladium (0) (26 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (1.5 mL) were added, and the mixture was stirred under heating reflux for 17 hours. Thereafter, toluene was added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried using anhydrous sodium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then purified by crystallization using a mixed solvent of toluene and methanol. Thereafter, the resultant was dried under reduced pressure at 50 ° C. overnight to obtain metal complex M3 (370 mg, yield 77%) as a red solid. The HPLC area percentage value of the metal complex M3 was 99.5% or more.

LC / MS (APCI positive): m / z = 2670 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.13 (d, 3 H), 8.81 (d, 6 H), 8. 70 (dd, 3 H), 8.24 (d , 3H), 8.19 (d, 3H), 8.12 (dd, 6H), 7.90 (dd, 6H), 7.79-7.74 (mult, 15H), 7.70-7. 66 (mult, 12H), 7.53-7.35 (mult, 33H), 7.28 (d, 3H), 1.36 (s, 54H).

  Example 4 Synthesis of Metal Complex M4

  The interior of the reaction vessel was shielded from light by an argon gas atmosphere, then metal complex M2 (1.27 g), compound M4a (1.04 g), tetrahydrofuran (70 mL), tetrakis (triphenylphosphine) palladium (0) (94 mg) and 20 A wt% aqueous solution of tetraethylammonium hydroxide (5.5 mL) was added, and the mixture was stirred for 19 hours while heating under reflux. Thereafter, toluene was added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried using anhydrous sodium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then purified by crystallization using a mixed solvent of toluene and methanol. Thereafter, the resultant was dried under reduced pressure at 50 ° C. overnight to obtain a metal complex M4 (1.16 g, yield 64%) as a red solid. The HPLC area percentage value of the metal complex M4 was 99.5% or more. Compound M4a was synthesized by the same method as compound L4e described later.

LC / MS (APCI positive): m / z = 2712 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.02 (d, 3 H), 8.76 (d, 6 H), 8.59 (dd, 3 H), 8.13 (d , 3H), 8.09-8.05 (mult, 9H), 7.77-7.72 (mult, 12H), 7.56 (s, 6H), 7.48-7.28 (mult, 45H) ) 7.18 (d, 3 H), 2. 15 (s, 9 H), 1. 36 (s, 54 H).

  Example 5 Synthesis of Compound L5

(Stage 1: Synthesis of Compound L5c)
The reaction vessel was changed to an argon gas atmosphere, and compound L5a (15 g), compound L5b (24 g), tetrahydrofuran (430 mL), ion-exchanged water (21 mL), bis (triphenylphosphine) palladium (II) dichloride (3.6 g) ) And cesium carbonate (250 g) were added and stirred at 60 ° C. for 64 hours. After that, toluene (400 mL) was added thereto and filtered using celite. The resulting filtrate was washed with 5% by weight brine. The obtained organic layer was dried over anhydrous sodium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then dried under reduced pressure to obtain compound L5c (20 g, yield 82%) as a yellow oil.

TLC / MS (DART positive): m / z = 290 [M + H] ⁺

(Stage 2: Synthesis of Compound L5e)
The reaction vessel was changed to an argon gas atmosphere, and then compound L5c (9.4 g), compound L5d (12 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (2. 7 g), potassium acetate (19 g) and 1,2-dimethoxyethane (100 mL) were added and stirred at 80 ° C. for 3 hours. After that, toluene (150 mL) was added thereto, and the mixture was filtered using celite, and the obtained filtrate was concentrated under reduced pressure. To the resulting residue was added hexane (180 mL) to dissolve it, this was filtered, and the obtained filtrate was concentrated. After that, toluene (70 mL) and acetonitrile (70 mL) were added thereto, and the mixture was filtered using silica gel, and the obtained filtrate was concentrated under reduced pressure. Thereafter, hexane (60 mL) and activated carbon (7.5 g) were added thereto, and the mixture was stirred at 50 ° C. for 1 hour. After that, the resultant was filtered using celite, and the obtained filtrate was concentrated under reduced pressure to obtain compound L5e (12 g) as a colorless oil.

TLC / MS (DART positive): m / z = 338 [M + H] ⁺

(Stage 3: Synthesis of Compound L5)
The reaction vessel was changed to an argon gas atmosphere, and compound L5e (8.8 g), compound M1b (11 g), 1,4-dioxane (450 mL), ion-exchanged water (24 mL), tetrakis (triphenylphosphine) palladium (0 g) ) (1.6 g) and cesium carbonate (70 g) were added and stirred at 90 ° C. for 3 hours. Thereafter, toluene was added thereto, and the mixture was filtered using celite, and the obtained filtrate was concentrated under reduced pressure. Thereafter, toluene was added thereto, and the obtained organic layer was washed with 5 wt% brine. The obtained organic layer was dried using anhydrous sodium sulfate and filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography using a mixed solvent of toluene and hexane, and then the solvent was evaporated under reduced pressure. After that, toluene (100 mL) and activated carbon (3.6 g) were added thereto, and the mixture was stirred at 60 ° C. for 1 hour. After that, toluene (250 mL) was added thereto, and after stirring, it was filtered using celite, and the obtained filtrate was concentrated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of toluene and methanol, and then dried under reduced pressure to obtain compound L5 (9.9 g, yield 69%) as a white powder. The HPLC area percentage value of compound L5 was 99.5% or more.

TLC / MS (DART positive): m / z = 543 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 10.01 (dd, 1 H), 9.25-9.21 (mult, 2 H), 9.05 (dd, 1 H), 8 .61 (dd, 2H), 8.25 (t, 1H), 8.14 (d, 2H), 8.04-7.99 (mult, 4H), 7.96 (dt, 1H), 7.. 74-7.45 (mult, 7H), 1.43 (s, 9H).

  Example 6 Synthesis of Metal Complex M5

(Stage 1: Synthesis of metal complex M5a)
The inside of the reaction vessel shielded from light was changed to an argon gas atmosphere, and then Compound L5 (736 mg) and 2-ethoxyethanol (13 mL) were added, and the temperature was raised to 90 ° C. Thereafter, iridium (III) chloride hydrate (273 mg) dissolved in ion exchanged water (5.4 mL) was added thereto, and the mixture was stirred at 105 ° C. for 21 hours. The resulting reaction mixture was cooled to room temperature, added to methanol (50 mL), and stirred at room temperature for 1 hour. Thereafter, the residue was filtered and dried under reduced pressure to obtain a red solid (850 mg) containing the metal complex M5a.

LC / MS (ESI positive): m / z = 2660 [M + K] ⁺

(Stage2a)
The inside of the reaction vessel protected from light was changed to an argon gas atmosphere, then a red solid (834 mg) containing metal complex M5a, silver (I) trifluoromethanesulfonate (207 mg) and acetonitrile (15 mL) were added and stirred at 90 ° C. for 2 hours . The resulting reaction mixture was cooled to room temperature, filtered using celite and alumina, and the obtained filtrate was concentrated under reduced pressure. Thereafter, hexane was added thereto and stirred. The resulting precipitate was collected by filtration to give a reddish orange solid (800 mg).

(Stage 2b: synthesis of metal complex M5)
The inside of the reaction vessel protected from light was changed to an argon gas atmosphere, and then the reddish orange solid (769 mg) obtained in Stage 2a above, compound L5 (1.2 g), 2,6-lutidine (660 mg) and diethylene glycol dimethyl ether (17 mL) In addition, it was stirred at 150 ° C. for 21 hours. The resulting reaction mixture was cooled to room temperature, added to methanol (50 mL), and stirred at room temperature for 1 hour. Then, this was filtered, toluene (50 mL) was added to the obtained residue, and it stirred and filtered. The obtained precipitate was dissolved in chloroform (300 mL), filtered using silica gel, and the obtained filtrate was concentrated under reduced pressure. Thereafter, methanol was added thereto, stirred and filtered. The obtained precipitate was dried under reduced pressure at 50 ° C. overnight to obtain metal complex M5 (450 mg) as a red solid. The HPLC area percentage value of the metal complex M5 was 99.0%.

LC / MS (ESI positive): m / z = 1856 [M + K] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.04 (d, 3 H), 8.79 (d, 6 H), 8.62 (dd, 3 H), 8.06 (dd) , 6H), 8.02 (d, 3H), 7.85 (d, 3H), 7.79-7.72 (mult, 12H), 7.48-7.35 (mult, 18H), 7. 05 (dd, 3 H), 6.86 (d, 3 H), 1. 36 (s, 27 H).

  Example 7 Synthesis of Compound L4

(Stage 1: Synthesis of Compound L4c)
After making the inside of a reaction vessel into a nitrogen gas atmosphere, compound L4a (50 g), compound L4b (75 g), toluene (500 mL), ion-exchanged water (500 mL), tetrakis (triphenylphosphine) palladium (0) (1.2 g) And sodium carbonate (85 g) were added and stirred at 90 ° C. for 5 hours. After cooling to room temperature, the obtained reaction solution was filtered using celite, and the obtained filtrate was washed with ion exchanged water. Activated carbon (5 g) was added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour, filtered using celite, and the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was purified by crystallization using a mixed solvent of toluene and methanol, and then dried under reduced pressure to obtain compound L4c (65 g, yield 91%) as a white solid. The HPLC area percentage value of compound L4c was 99.5% or more.

TLC / MS (DART positive): m / z = 357 [M + H] ⁺

(Stage 2: Synthesis of Compound L4e)
The reaction vessel was changed to a nitrogen gas atmosphere, and compound L4c (61 g), compound L4d (550 mg), cyclopentyl methyl ether (490 mL), (1,5-cyclooctadiene) (methoxy) iridium (I) dimer ( 680 mg) and compound L5d (54 g) were added and stirred at 105 ° C. for 4 hours. The resulting reaction mixture was cooled to room temperature, then added to methanol (920 mL), stirred and filtered. The obtained solid was dissolved in toluene (750 mL), activated clay (7.5 g) was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, it filtered using silica gel and the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was purified by crystallization using a mixed solvent of toluene and methanol, and then dried under reduced pressure to obtain compound L4e (70 g, yield 85%) as a white solid. The HPLC area percentage value of compound L4e was 99.5% or more.

LC / MS (ESI positive): m / z = 521 [M + K] ⁺

(Stage 3: Synthesis of Compound L4g)
After the inside of the reaction vessel was changed to a nitrogen gas atmosphere, compound L4e (69 g), compound L4f (41 g), toluene (690 mL), tetrakis (triphenylphosphine) palladium (0) (1.7 g) and 20% by weight tetraethylammonium hydroxy An aqueous solution of doe (420 g) was added and stirred at 85 ° C. for 2 hours. After that, toluene (280 mL) was added thereto, the obtained organic layer was washed with ion exchanged water, and the obtained organic layer was concentrated under reduced pressure. The obtained residue was purified by crystallization using a mixed solvent of toluene and methanol, and then dried under reduced pressure at 50 ° C. overnight to obtain 4 g (66 g, yield 90%) of a compound L as a white solid. The HPLC area percentage value of 4 g of compound L was 96.0%.

LC / MS (ESI positive): m / z = 549 [M + K] ⁺

(Stage 4: Synthesis of Compound L4h)
The reaction vessel is changed to a nitrogen gas atmosphere, and then Compound L 4 g (66 g), Compound L 5 d (39 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (2.1 g) Then, potassium acetate (38 g) and 1,2-dimethoxyethane (DME) (650 mL) were added and stirred at 85 ° C. for 2 hours. The obtained reaction solution was cooled to room temperature, toluene (330 mL) was added, and the mixture was filtered using celite, and the obtained filtrate was washed with ion-exchanged water. The obtained organic layer was concentrated under reduced pressure, toluene (550 mL) and activated carbon (9.8 g) were added, and the mixture was stirred at room temperature for 1 hour. Then, it filtered using celite, the obtained filtrate was wash | cleaned with ion-exchange water, and the obtained organic layer was concentrated under reduced pressure. The resulting residue is purified by crystallization using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure overnight at 50 ° C. to give compound L4h (57 g, yield 80%) as a white solid Got as. The HPLC area percentage value of compound L4h was 99.5% or more.

LC / MS (ESI positive): m / z = 597 [M + K] ⁺

(Stage 5: Synthesis of Compound L4j)
After making the inside of a reaction vessel into a nitrogen gas atmosphere, compound L4h (57 g), compound L4i (24 g), toluene (570 mL), tetrakis (triphenylphosphine) palladium (0) (1.2 g) and 20% by weight tetraethylammonium hydroxy An aqueous solution of doe (300 g) was added and stirred at 64.degree. C. for 4 hours. The resulting reaction solution was cooled to 5 ° C., stirred at 5 ° C. for 1 hour, and filtered. The obtained filtrate was washed with ion exchanged water, and the obtained organic layer was concentrated under reduced pressure. The resulting residue is purified by recrystallization using a mixed solvent of toluene and methanol, and then dried under reduced pressure at 50 ° C. overnight to give compound L4j (45 g, yield 74%) as a white solid. The The HPLC area percentage value of compound L4j was 97.6%.

LC / MS (ESI positive): m / z = 588 [M + H] ⁺

(Stage 6: Synthesis of Compound L4k)
The reaction vessel is changed to a nitrogen gas atmosphere, and then compound L4j (44 g), compound L5d (23 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.2 g) Then, potassium acetate (22 g) and 1,2-dimethoxyethane (DME) (440 mL) were added and stirred at 85 ° C. for 3 hours. The obtained reaction solution is cooled to room temperature, toluene (330 mL) is added, and the mixture is filtered using celite, and the obtained filtrate is washed with ion exchanged water, and the obtained organic layer is concentrated under reduced pressure. After that, toluene (750 mL) and activated carbon (6.6 g) were added thereto, and the mixture was stirred at room temperature for 1 hour and then filtered using celite. The obtained filtrate was washed with ion exchanged water, and the obtained organic layer was concentrated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure overnight at 50 ° C. to give compound L4k (41 g, yield 86%) as a white solid . The HPLC area percentage value of compound L4k was 98.7%.

LC / MS (ESI positive): m / z = 636 [M + H] ⁺

(Stage 7: Synthesis of Compound L4)
After the inside of the reaction vessel was changed to a nitrogen gas atmosphere, compound L4k (15 g), compound M1b (10 g), toluene (300 mL), tetrakis (triphenylphosphine) palladium (0) (270 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (70 g) was added and stirred at 70 ° C. for 1 hour. The resulting reaction solution was cooled to room temperature and filtered through celite, and toluene (60 mL) was added to the obtained filtrate. The obtained organic layer was washed with ion exchanged water, and the obtained organic layer was concentrated under reduced pressure. After that, toluene (320 mL) and activated carbon (2.3) were added thereto, and the mixture was stirred at room temperature for 30 minutes and filtered using silica gel, and the obtained filtrate was evaporated under reduced pressure. The resulting residue is crystallized using a mixed solvent of ethyl acetate and acetonitrile, then purified by washing with n-heptane and then dried under reduced pressure overnight at 50 ° C. to give compound L4. (17 g, 83% yield) was obtained as a white solid. The HPLC area percentage value of compound L4 was 99.5% or more.

LC / MS (APCI positive): m / z = 841 [M + H] ^+
1 H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 10.29 (d, 1 H), 9.25 (d, 2 H), 9.05 (dd, 1 H), 8.62 (d, 2 H) ), 8.41 (s, 1 H), 8.11 (d, 3 H), 8.02-7.97 (mult, 3 H), 7.77 (d, 1 H), 7.71-7. mult, 9H), 7.48 (d, 4H), 7.39 (d, 4H), 2.21 (s, 3H), 1.40 (s, 18H).

  Example 8 Synthesis of Metal Complex M4 (Part 2)

(Stage 1: Synthesis of metal complex M4a)
The inside of the reaction vessel shielded from light was changed to a nitrogen gas atmosphere, and then Compound L4 (16 g) and 2-ethoxyethanol (210 mL) were added, and the temperature was raised to 95 ° C. Thereafter, iridium (III) chloride hydrate (3.1 g) dissolved in ion exchanged water (27 mL) was added thereto, and the mixture was stirred at 120 ° C. for 4 hours. After distilling off the mixture (150 mL) of water and 2-ethoxyethanol from the reaction liquid obtained, 2-ethoxyethanol (150 mL) was added and it stirred at 125 degreeC for 16 hours. The resulting reaction mixture was cooled to room temperature, methanol (70 mL) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, it was filtered and the obtained residue was dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of toluene and n-hexane, and then dried under reduced pressure to obtain a metal complex M4a (11 g) as a red solid. The HPLC area percentage value of the metal complex M4a was 98.1%.

LC / MS (ESI positive): m / z = 1946 [M + 2K] ²⁺

(Stage 2: Synthesis of metal complex M4)
After making the inside of the reaction vessel shielded from light a nitrogen gas atmosphere, metal complex M4a (10 g), compound L4 (4.5 g), silver (I) trifluoromethanesulfonate (1.8 g), 2,6-lutidine (740 mg) And diethylene glycol dimethyl ether (115 mL) were added and stirred at 150 ° C. for 2 hours. The resulting reaction mixture was cooled to room temperature, methanol (450 mL) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the resultant was filtered, and the obtained solid was dissolved in toluene (230 mL), followed by filtration using silica gel, and the obtained filtrate was concentrated under reduced pressure. The resulting residue is purified by silica gel column chromatography using a mixed solvent of toluene and n-hexane, then purified by crystallization using toluene and acetonitrile, and then dried under reduced pressure overnight at 50 ° C. This gave metal complex M4 (7.2 g, yield 91%) as a red solid. The HPLC area percentage value of the metal complex M4 was 98.3%.

LC / MS (APCI positive): m / z = 2712 [M + H] ^+
1 H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 9.02 (d, 3 H), 8.76 (d, 6 H), 8.59 (dd, 3 H), 8.13 (d , 3H), 8.09-8.05 (mult, 9H), 7.77-7.72 (mult, 12H), 7.56 (s, 6H), 7.48-7.28 (mult, 45H) ) 7.18 (d, 3 H), 2. 15 (s, 9 H), 1. 36 (s, 54 H).

<Comparative example 2> The synthesis | combination of metal complex CM1 Metal complex CM1 was synthesize | combined according to the method as described in Unexamined-Japanese-Patent No. 2010-43243.

<Comparative example 2> The synthesis | combination of metal complex CM2 Metal complex CM2 was synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2011-105701.

<Comparative example 3> The synthesis | combination of metal complex CM3 Metal complex CM3 was synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2006-188673.

<Measurement Example 1> Measurement of PLQY and Emission Spectrum of Metal Complex M3 Measurement of PLQY and emission spectrum was performed using a xylene solution (0.0008% by weight) of metal complex M3. The emission having the maximum peak of the emission spectrum at 615 nm was observed, and the PLQY was 71%.

<Measurement Example 2> Measurement of PLQY and Emission Spectrum of Metal Complex M4 The PLQY and emission spectrum of the metal complex M4 synthesized in Example 4 were measured using a xylene solution (0.0008% by weight). The emission having the maximum peak of the emission spectrum at 622 nm was observed, and the PLQY was 67%.

<Measurement Example 3> Measurement of PLQY and Emission Spectrum of Metal Complex M5 Measurement of PLQY and emission spectrum was performed using a xylene solution (0.0008 wt%) of metal complex M5. The emission having the maximum peak of the emission spectrum at 626 nm was observed, and the PLQY was 59%.

<Measurement Example C1> Measurement of PLQY and Emission Spectrum of Metal Complex CM1 Measurement of PLQY and emission spectrum was performed using a xylene solution (0.0008 wt%) of metal complex CM1. The emission having the maximum peak of the emission spectrum at 598 nm was observed, and the PLQY was 66%.

<Measurement Example C2> Measurement of PLQY and Emission Spectrum of Metal Complex CM2 PLQY and emission spectrum were measured using a xylene solution (0.0008% by weight) of metal complex CM2. The emission having the maximum peak of the emission spectrum at 613 nm was observed, and the PLQY was 59%.

<Measurement Example C3> Measurement of PLQY and Emission Spectrum of Metal Complex CM3 PLQY and emission spectrum were measured using a xylene solution (0.0008 wt%) of metal complex CM1. The emission having the maximum peak of the emission spectrum at 625 nm was observed, and the PLQY was 57%.

  As shown in FIG. 1 showing the relationship between PLQY and the maximum peak wavelength of the emission spectrum of metal complexes M3 to M5 and metal complexes CM1 to CM3, the metal complex of the present invention is a metal complex that exhibits red phosphorescence, It turns out that it is a metal complex which is excellent in a quantum yield.

Claims (10)

Metal complexes represented by the following formula (1) (wherein the following Ir (L39) ₃ , Ir (L 48) ₃ , Ir (L 57) ₃ , Ir (L 76) ₃ , Ir (L 78) ₃ , Ir (L 79) _{3, Ir (L104) 3,} except _{Ir (L108) 3, Ir (} L131) 3, I r (L176) 3, I r (L209) 3, Ir (L216) 3 and Ir _{(L222) 3.).}

[In the formula,
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group in which two or more rings are fused, or a heterocyclic group in which two or more rings are fused, and these groups have a substituent It may be When a plurality of Ar ¹ and Ar ² exist, they may be the same or different.
R ¹¹ and R ¹² 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 monovalent heterocyclic group or a substituted amino group , The group may have a substituent. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group . When a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are present, they may be the same or different. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ respectively combine to form a ring with the carbon atom to which each is attached May be ]

The metal complex according to claim 1, wherein Ar ¹ and Ar ² are aromatic hydrocarbon groups represented by the following formula (2-1) or (2-2).

[In the formula,
R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group . Plural R ^{2 s} may be the same or different, and adjacent R ^{2 s} may be bonded to each other to form a ring together with the atoms to which they are bonded. ] At least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group represented by the following formula (D-A) or (D-B) Item 3. The metal complex according to item 1 or 2.

[In the formula,
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
G ^DA represents an aromatic hydrocarbon group, and this group may have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group, and this group may have a substituent. When a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 exist, they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. The plurality of T ^DA may be the same or different. ]

[In the formula,
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
G ^DA represents an aromatic hydrocarbon group, and this group may have a substituent. A plurality of G ^DA 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, and this group may have a substituent. When a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are present, they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. The plurality of T ^DA may be the same or different. ] At least one selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group represented by the following formula (3-1) or (3-2) Item 3. The metal complex according to Item 3.

[In the formula,
R ³¹ , R ³² and R ³³ 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 monovalent heterocyclic group or a substituted amino group . When a plurality of R ³¹ are present, they may be the same or different, and a plurality of R ³² may be the same or different, and a plurality of R ³³ may be the same or different. ] The metal complex according to claim 3 or 4, wherein R ¹⁴ is a group represented by the formula (D-A) or (D-B). The metal complex according to claim 5, wherein the R ¹⁴ is a group represented by the formula (3-1) or (3-2). The metal complex as described in any one of Claims 1-6 whose said R < ¹¹ >, R < ¹² >, R <^13> , R <^15> and R <^16> is a hydrogen atom. The metal complex according to any one of claims 1 to 7;
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 solvents. The light emitting element obtained by using the metal complex as described in any one of Claims 1-7 for a light emitting layer . A compound represented by the following formula (1M) (provided that the following L39, L48, except L57, L76, L78, L79, L104, L108, L131, and L 176, L 209, L216 and L222.).

[In the formula,
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group in which two or more rings are fused, or a heterocyclic group in which two or more rings are fused, and these groups have a substituent It may be
R ¹¹ and R ¹² 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 monovalent heterocyclic group or a substituted amino group , The group may have a substituent. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group . R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ respectively combine to form a ring with the carbon atom to which each is attached May be ]

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