JP2017052709A - Metal complex and light emitting element comprising metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triplet light emitting metal complex that can achieve a white luminescent color having an excellent color rendering property.SOLUTION: The present invention provides a metal complex represented by formula (1), where nis an integer of 1-3; nis 0 or 1; R-Rindependently represent H, an alkyl group, an aryl group, heteroaryl group or the like; Rand R, Rand R, Rand R, Rand R, Rand R, and Rand Rmay form a ring together with C to which they bond, respectively; at least one of Rand Ris F, an alkyl group having F or the like; at least one selected from R, R, R, and Ris a group having a specific substituent; A-G-Aare an anionic bidentate ligand; Aand Aindependently represent C, O, N].SELECTED DRAWING: None

Description

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

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

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

  However, in the light emitting element including the metal complex according to the above prior art document, it is difficult to realize a white light emitting color with high color rendering properties.

  In view of the above, an object of the present invention is to provide a metal complex capable of realizing a white color with high color rendering properties in a light-emitting element, and thus to provide a composition containing the metal complex and a light-emitting element including the metal complex. To do.

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

［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。］

［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。］
［２］ 前記Ｒ^４およびＲ^５のいずれか一方がフッ素原子を置換基として有するアルキル基である、［１］に記載の金属錯体。
［３］ 前記Ｒ^４およびＲ^９からなる群から選ばれる少なくとも１つが、前記式（Ｄ−Ａ）で表される基である、［１］または［２］に記載の金属錯体。
［４］ 前記式（Ｄ−Ａ）で表される基が、下記式（Ｄ−Ａ１）、（Ｄ−Ａ２）または（Ｄ−Ａ３）で表される基である、［１］〜［３］のいずれか１つに記載の金属錯体。

［式中、
Ｒ^ｐ１、Ｒ^ｐ２およびＲ^ｐ３は、それぞれ独立に、アルキル基、シクロアルキル基またはハロゲン原子を表す。Ｒ^ｐ１およびＲ^ｐ２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。
ｎｐ１は、１〜５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。複数存在するｎｐ１は、同一でも異なっていてもよい。］
［５］ 前記式（Ｄ−Ａ）で表される基が、前記式（Ｄ−Ａ１）で表される基である、［４］に記載の金属錯体。
［６］ 前記ｎ_２が１である、［１］〜［５］のいずれか１つに記載の金属錯体。
［７］ 前記ｎ_１が３である、［１］〜［６］のいずれか１つに記載の金属錯体。
［８］ ［１］〜［７］のいずれか１つに記載の金属錯体と、
下記式（Ｈ−１）で表される化合物とを含有する組成物。

［式（Ｈ−１）中、
Ａｒ^Ｈ１およびＡｒ^Ｈ２は、それぞれ独立に、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。
ｎ^Ｈ１およびｎ^Ｈ２は、それぞれ独立に、０または１を表す。ｎ^Ｈ１が複数存在する場合、それらは同一でも異なっていてもよい。ｎ^Ｈ２が複数存在する場合、それらは同一でも異なっていてもよい。
ｎ^Ｈ３は、０以上の整数を表す。
Ｌ^Ｈ１は、アリーレン基、２価の複素環基、または、−［Ｃ（Ｒ^Ｈ１１）_２］ｎ^Ｈ１１−で表される基を表し、これらの基は置換基を有していてもよい。Ｌ^Ｈ１が複数存在する場合、それらは同一でも異なっていてもよい。
ｎ^Ｈ１１は、１以上１０以下の整数を表す。Ｒ^Ｈ１１は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Ｈ１１は、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。
Ｌ^Ｈ２は、−Ｎ（−Ｌ^Ｈ２１−Ｒ^Ｈ２１）−で表される基を表す。Ｌ^Ｈ２が複数存在する場合、それらは同一でも異なっていてもよい。
Ｌ^Ｈ２１は、単結合、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^Ｈ２１は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］
［９］ ［１］〜［７］のいずれか１つに記載の金属錯体と、
正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料、酸化防止剤および溶媒からなる群より選ばれる少なくとも１種の材料と
を含有する組成物。
［１０］ ［１］〜［７］のいずれか１つに記載の金属錯体を含む発光素子。 The present invention has been made in view of the above problems, and provides the following [1] to [10].
[1] A metal complex represented by the following formula (1).

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

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

[Where:
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent. A plurality of ^GDA may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDAs may be the same or different. ]
[2] The metal complex according to [1], wherein any one of R ⁴ and R ⁵ is an alkyl group having a fluorine atom as a substituent.
[3] The metal complex according to [1] or [2], wherein at least one selected from the group consisting of R ⁴ and R ⁹ is a group represented by the formula (DA).
[4] The group represented by the formula (DA) is a group represented by the following formula (D-A1), (D-A2) or (D-A3), [1] to [3 ] The metal complex as described in any one of.

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group or a halogen atom. When a plurality of R ^p1 and R ^p2 are present, they may be the same or different.
np1 represents an integer of 1 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]
[5] The metal complex according to [4], wherein the group represented by the formula (DA) is a group represented by the formula (D-A1).
[6] The metal complex according to any one of [1] to [5], wherein n ₂ is 1.
[7] The metal complex according to any one of [1] to [6], wherein n ₁ is 3.
[8] The metal complex according to any one of [1] to [7],
The composition containing the compound represented by a following formula (H-1).

[In the formula (H-1),
Ar ^H1 and Ar ^H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
n ^H1 and n ^H2 each independently represent 0 or 1. When a plurality of n ^H1 are present, they may be the same or different. When a plurality of n ^H2 are present, they may be the same or different.
n ^H3 represents an integer of 0 or more.
L ^H1 represents an arylene group, a divalent heterocyclic group, or a group represented by — [C (R ^H11 ) ₂ ] n ^H11 —, and these groups optionally have a substituent. When a plurality of L ^H1 are present, they may be the same or different.
n ^H11 represents an integer of 1 or more and 10 or less. R ^H11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^H11 may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
L ^H2 represents a group represented by -N (-L ^H21 -R ^H21 )-. When a plurality of L ^H2 are present, they may be the same or different.
L ^H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. R ^H21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]
[9] The metal complex according to any one of [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 a solvent.
[10] A light emitting device comprising the metal complex according to any one of [1] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, the metal complex which can implement | achieve the white luminescent color excellent in the color rendering property in a light emitting element can be provided.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[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, near ultraviolet irradiation treatment, visible light irradiation treatment, infrared irradiation treatment, radical reaction, etc. Preferably, it is group represented by either of formula (B-1)-(B-17). These groups may have a substituent.

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

  “Dendron” means a group having a regular dendritic branched structure having an atom or ring as a branching point (ie, a dendrimer structure). Examples of the compound having dendron (hereinafter referred to as “dendrimer”) include, for example, International Publication No. 2002/066733, Japanese Patent Application Laid-Open No. 2003-231692, International Publication No. 2003/079736, International Publication No. 2006/097717. And the structure described in the literature.

  The dendron is preferably a group represented by the formula (DA) or (DB).

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

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

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

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

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

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

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

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

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

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

[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 (D-A1) to (D-A3), more preferably a group represented by the formula (D-A1). is there.

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

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

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

  np1 is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and even more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.

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

In formula (D-A1) to formula (D-A3) and formula (D-B1) to formula (D-B3), at least one of a plurality of R ^p1 is an alkyl group having 4 or more carbon atoms ^{Alternatively} , it is preferably a cycloalkyl group having 4 or more carbon atoms, and all of the plurality of R ^p1 are alkyl groups having 4 or more carbon atoms, or cycloalkyl groups having 4 or more carbon atoms. Preferably there is.

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

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

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

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

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

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

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

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

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

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

In formula (1), R ^{1 to} R ⁶ and R ^{8 to} R ¹⁰ can improve the solubility and film-forming property of the metal complex of the present invention in a solvent, and are preferably a hydrogen atom, an alkyl group, a cyclohexane. It is an alkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, still more preferably a hydrogen atom. Here, at least one selected from the group consisting of R ⁴ and R ⁵ , in other words, either or both of R ⁴ and R ⁵ are an alkyl group having a fluorine atom as a substituent, and a fluorine atom as a substituent. A cycloalkyl group having a fluorine atom as a substituent, a cycloalkoxy group having a fluorine atom as a substituent, an aryl group having a fluorine atom as a substituent, an aryloxy group having a fluorine atom as a substituent, a fluorine atom A monovalent heterocyclic group, fluorine atom or cyano group as a substituent, preferably an alkyl group, fluorine atom or cyano group having a fluorine atom as a substituent. Among them, since the durability of the metal complexes of the present invention is excellent, it is preferable that either one of R ⁴ and R ⁵ is an alkyl group, a fluorine atom or a cyano group having a fluorine atom as a substituent, R ⁴ And R ⁵ is more preferably an alkyl group having a fluorine atom as a substituent, R ⁴ is an alkyl group having a fluorine atom as a substituent, or R ⁵ is a fluorine atom. Particularly preferred. Furthermore, at least one selected from the group consisting of R ⁴ , R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (DA) or (D—B), preferably R ⁴ , At least one selected from the group consisting of R ⁸ , R ⁹ and R ¹⁰ is a group represented by the formula (DA).

At least one selected from the group consisting of R ⁴ and R ⁹ is preferably a group represented by the formula (DA) or (DB), and at least selected from the group consisting of R ⁴ and R ⁹ It is more preferable that one is a group represented by the formula (DA), and it is more preferable that either one of R ⁴ and R ⁹ is a group represented by the formula (DA). .

In formula (1), R ⁷ and R ¹¹ can make the emission color of the metal complex of the present invention closer to pure blue, in other words, the maximum peak wavelength of the emission spectrum of the metal complex can be present on the shorter wavelength side. Therefore, an alkyl group or a cycloalkyl group is preferable, and an alkyl group is more preferable. The emission color that is pure blue usually means an emission color in which the maximum peak wavelength of the emission spectrum is in the range of 420 to 465 nm and the width of the peak existing in the wavelength of 420 to 465 nm is 100 nm or less. To do.

In formula (1), R ⁹ is preferably a group represented by formula (DA), a group represented by formula (DB), an aryl group or a monovalent heterocyclic group. A group represented by (DA), a group represented by formula (DB), or an aryl group is more preferred, and a group represented by formula (DA), formula (DB) Or a phenyl group is more preferred. The aryl group represented by R ⁹ (for example, phenyl group) and the monovalent heterocyclic group may have a substituent, and the substituent is preferably an alkyl group or a cycloalkyl group.

  Examples of the metal complex represented by the formula (1) include metal complexes represented by the following formulas (Ir-1)-(Ir-29), and the lifetime of the light-emitting element including the metal complex of the present invention is long. Since it is particularly excellent, it is preferably a metal complex represented by the formulas (Ir-1) to (Ir-13), more preferably a metal complex represented by the formulas (Ir-1) to (Ir-9). It is.

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

In formulas (Ir-1) to (Ir-29), R _L is preferably a group represented by any one of groups II of formulas (II-01) to (II-06).
<Group II>

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

  As the metal complex represented by the formula (1), plural kinds of geometric isomers can be considered, and the metal complex represented by the formula (1) may be any geometric isomer. Since the metal complex represented by the formula (1) can improve the luminance lifetime of the light-emitting element, the metal complex represented by the formula (1) in the facial form is preferable, and represented by the formula (1) in the facial form. The proportion of the metal complex is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 99 mol% or more, particularly preferably 100 mol, based on the total amount of the metal complex. %.

  According to a preferred embodiment of the metal complex of the present invention, a metal complex having excellent stability can be provided.

<Method for producing metal complex>
・ Production method 1
The metal complex of the present invention can be produced, for example, by a production method in which a ligand compound and a metal compound are reacted. You may perform the functional group conversion reaction of the ligand of a metal complex as needed.

The compound represented by the formula (1) includes, for example, a step A in which a compound represented by the following formula (M-1) is reacted with an iridium compound or a hydrate thereof, and the following formula (M-2) And a step B of reacting the metal complex represented by formula (M-1) with the ligand represented by the compound represented by formula (M-1) or the ligand represented by A ¹ -G ¹ -A ^2. Can be manufactured.

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

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

  Step A and Step B are usually performed in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol, and 2-ethoxyethanol; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, and diglyme. Halogenated 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 solvent; acetone, dimethyl sulfoxide, water and the like.

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

  The amount of the compound represented by the formula (M-1) used in Step A is usually 2 to 20 mol with respect to 1 mol of the iridium compound or its hydrate.

The amount of the compound represented by the formula (M-1) or the precursor of the ligand represented by A ¹ -G ¹ -A ² used in Step B is represented by the formula (M-2). It is 1-100 mol normally with respect to 1 mol of metal complexes.

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

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

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

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

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

W ¹ is preferably -B (OR ^W1 ) _{2 because} ^{W 1} can facilitate the coupling reaction between the compound represented by Formula (2) and the compound represented by Formula (M-3). A trifluoromethanesulfonyloxy group, a bromine atom or an iodine atom, more preferably a group represented by the formula (W-7).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The metal complex represented by the formula (3c) or the formula (3d) which is one embodiment of the metal complex represented by the formula (3) is, for example, a compound represented by the formula (5) according to the following scheme Can be synthesized from

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

  More specifically, the metal complex represented by the formula (3c) can be synthesized by, for example, the step E in which the compound represented by the formula (5) is reacted with the iridium compound in an organic solvent. Step E can be performed by a reaction similar to Step A and Step B of Production Method 1 already described.

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

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

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

・ Production method 3
The compound represented by the formula (1), when n ₁ is 3, includes, for example, a step G in which a compound represented by the formula (M-1) shown in the following scheme is reacted with an iridium compound. It can be synthesized by the method.

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

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

  Step G is usually performed in a solvent, but may not be performed in a solvent. As a solvent, the solvent whose boiling point is 100-300 degreeC among the solvents already demonstrated about the process A and the process B is preferable.

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

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

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

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

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

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

  The compounds, catalysts, and solvents used in the reactions already described in the above <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 is such a composition by forming a composition with a host material having at least one function selected from the group consisting of hole injecting property, hole transporting property, electron injecting property, and electron transporting property. The external quantum efficiency of the light-emitting element containing s is particularly 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 the host material, the content of the metal complex of the present invention is usually 0.05 when the total of the metal complex of the present invention and the host material is 100 parts by weight. It is -80 weight part, Preferably it is 0.1-50 weight part, More preferably, it is 0.5-40 weight part.

Since the lowest excited triplet state (T ₁ ) of the host material can further improve the external quantum efficiency of the obtained light-emitting element, is the energy level equivalent to T ₁ of the metal complex of the present invention? Or a higher energy level.

  As the host material, since the light-emitting element to be obtained can be manufactured by a coating method using a coating liquid, a material that is soluble in a solvent capable of dissolving the metal complex of the present invention is preferable. Hereinafter, the host material will be specifically described.

  Compounds that can serve as host materials are classified into low-molecular compounds and high-molecular compounds.

  A low molecular compound (hereinafter referred to as “low molecular host”) used as a host material will be described.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As a compound represented by a formula (H-1), the compound represented by the following formula (H-101)-a formula (H-118) is mentioned, for example.

  Examples of the polymer compound used as the host material (hereinafter referred to as “polymer host”) include a polymer compound that is a hole transport material described later and a polymer compound that is an electron transport material described later. .

[Polymer host]
A preferred polymer compound used as a host material will be described.

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

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

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

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

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

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

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

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

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

  Examples of the structural unit represented by the formula (Y) include structural units represented by the following formula (Y-1) to the following formula (Y-10) described later. The polymer host and the metal of the present invention From the viewpoint of the luminance lifetime of the light-emitting element using the composition containing the complex, it is preferably a structural unit represented by the following formula (Y-1) to the following formula (Y-3), and from the viewpoint of electron transport properties Is preferably a structural unit represented by the following formula (Y-4) to the following formula (Y-7), and preferably from the following formula (Y-8) to the following formula, from the viewpoint of hole transportability. It is a structural unit represented by (Y-10). Hereinafter, the structural units represented by Formula (Y-1) to Formula (Y-10) will be specifically described.

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

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

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

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

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

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

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

[Wherein, R ^Y1 represents the same meaning as described above. X ^Y1 represents a group represented by —C (R ^Y2 ) ₂ —, a group represented by —C (R ^Y2 ) ═C (R ^Y2 ) —, or C (R ^Y2 ) ₂ —C (R ^Y2 ) _2. -Represents a group represented by-. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

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

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

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

In ^XY1 , four R ^Y2 in the group represented by —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — are preferably an alkyl group or a cycloalkyl group which may have a substituent. It is. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded. When R ^Y2 forms a ring, —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — The group represented is preferably a group represented by the following formula (Y-B1) to the following formula (Y-B5), more preferably a group represented by the formula (Y-B3). The group may have a substituent.

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

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

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

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

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

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

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

  The structural units represented by the formula (Y-4) to the formula (Y-7) are structural units represented by the following formula (Y-4) to the following formula (Y-7).

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

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

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

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

  The structural units represented by the formula (Y-8) to the formula (Y-10) are structural units represented by the following formula (Y-8) to the following formula (Y-10).

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

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

  Examples of the structural unit represented by the formula (Y) include a structural unit composed of an arylene group represented by the following formula (Y-101) to the following formula (Y-121), and the following formula (Y-201) to the following. A structural unit comprising a divalent heterocyclic group represented by the formula (Y-206), at least one arylene group represented by the following formula (Y-301) to the following formula (Y-304), and at least one kind. And a structural unit composed of a divalent group in which the divalent heterocyclic group is directly bonded.

The structural unit represented by the formula (Y), wherein Ar ^Y1 is an arylene group, further improves the luminance life of a light-emitting element using a composition containing a polymer host and the metal complex of the present invention. Therefore, it is preferably 0.5 to 80 mol%, more preferably 30 to 60 mol%, based on the total amount of structural units contained in the polymer compound.

A structural unit represented by formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group, or at least one arylene group and at least one divalent heterocyclic group directly bonded to each other. The structural unit that is a group of the above can further improve the charge transport property of the light-emitting device using the composition containing the polymer host and the metal complex of the present invention, so the total of the structural units contained in the polymer compound Preferably it is 0.5-30 mol% with respect to quantity, More preferably, it is 3-20 mol%.

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

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

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

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

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

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

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

The divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 is more preferably represented by 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 an arylene group which may have a substituent.

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

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

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

As 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, at least represented by Ar ^Y1 in the formula (Y) Examples thereof include the same divalent groups in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.

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

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

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

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

  Since the structural unit represented by the formula (X) can further improve the hole transportability, it is preferably 0.1 to 50 mol% with respect to the total amount of the structural units contained in the polymer host. More preferably, it is 1-40 mol%, More preferably, it is 5-30 mol%.

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

  In the polymer host, only one type of structural unit represented by the formula (X) may be included, or two or more types of structural units may be included.

  Examples of the polymer host include polymer compounds (P-1) to (P-6) shown in Table 3 below. Here, the “other” structural unit means a structural unit other than the structural unit represented by the formula (Y) and the structural unit represented by the formula (X).

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

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

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

  In the polymerization method, examples of the method for charging the monomer include, for example, a method in which the entire amount of the monomer is charged into the reaction system at once, a part of the monomer is charged and reacted, and then the remaining monomer is charged. Examples thereof include a method of charging all at once, continuously or divided, a method of charging a monomer continuously or dividedly, and the like.

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

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

  The composition containing the metal complex and the solvent of the present invention can be used as a material for a coating liquid (hereinafter referred to as “ink”) or as the coating liquid itself. Ink can be used suitably for manufacture of the light emitting element by printing methods (coating method), such as an inkjet printing method and a nozzle printing method.

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

  The solvent contained in the ink is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink. Examples of the solvent include chlorinated solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as THF, dioxane, anisole and 4-methylanisole; toluene, xylene Aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Aliphatic hydrocarbon solvents such as n-dodecane and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetophenone; ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate; Polyhydric alcohol solvents such as glycol, glycerin 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. A solvent may be used individually by 1 type, or may use 2 or more types together.

  In ink, the compounding quantity of a solvent is 1000-100000 weight part normally with respect to 100 weight part of metal complexes of this invention, Preferably it is 2000-20000 weight part.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The light emitting material preferably comprises a triplet light emitting complex.

  In order to realize a white luminescent color having high color rendering properties in combination with the metal complex of the present invention, as a luminescent material different from the metal complex of the present invention, two or more types having a maximum peak wavelength of an emission spectrum of 495 nm or more and less than 750 nm It is preferable to further use a triplet luminescent complex of

  The color rendering properties can be evaluated by, for example, an average color rendering index Ra calculated from the emission spectrum by the method described in JIS Z8726-1990. When calculating the average color rendering index Ra, PL of one or more light-emitting materials (for example, two or more triplet light-emitting complexes) used in combination with the metal complex of the present invention and the metal complex of the present invention is used as an emission spectrum. You may use the spectrum obtained by measuring each spectrum and adding those PL spectra so that it may become a white emission spectrum.

  The emission color can be adjusted to white by adjusting the ratio between the metal complex of the present invention and the content of the two or more triplet light-emitting complexes.

  The light emission color of the light emitting element can be confirmed by measuring the light emission chromaticity of the light emitting element and obtaining chromaticity coordinates (CIE chromaticity coordinates). Here, the white luminescent color means a luminescent color in the vicinity of the color temperature 2500K to 7000K (correlated color temperature 2500K to 7000K) on the Plankian locus, and usually the X coordinate (CIE-x) of the CIE chromaticity coordinates. Is in the range of 0.25 to 0.55, and the Y coordinate (CIE-y) of the CIE chromaticity coordinate is in the range of 0.25 to 0.55. Preferably, the CIE chromaticity coordinate The X coordinate is in the range of 0.30 to 0.50, and the Y coordinate of the CIE chromaticity coordinate is in the range of 0.30 to 0.50.

  In order to adjust the emission color of a light-emitting element containing the metal complex of the present invention and the two or more triplet light-emitting complexes to white, the maximum peak wavelength of the emission spectrum of the metal complex of the present invention is preferably 400 nm. The thickness is 490 nm or more and more preferably 420 nm or more and 480 nm or less.

  In order to adjust the emission color of a light-emitting device containing the metal complex of the present invention and the two or more triplet light-emitting complexes to white, the maximum peak wavelength of the emission spectrum of two or more triplet light-emitting complexes is: Preferably they are 500 nm or more and 680 nm or less, More preferably, they are 505 nm or more and 630 nm or less.

  The maximum peak wavelength of the emission spectrum of the metal complex of the present invention and the maximum peak wavelength of the emission spectrum of the two or more triplet emission complexes are different from each other in order to adjust the emission color of the light emitting element to white. The difference is preferably 10 to 200 nm, more preferably 20 to 180 nm, and still more preferably 40 to 125 nm.

  In order to adjust the emission color of the resulting light emitting device to white when the maximum peak wavelength of the emission spectrum of the metal complex of the present invention is different from the maximum peak wavelength of the emission spectrum of the two or more triplet emission complexes. Of the two or more triplet luminescent complexes, the maximum peak wavelength of the emission spectrum of the triplet luminescent complex having the maximum peak wavelength of the emission spectrum on the shortest wavelength side is preferably 500 nm or more and less than 570 nm, more preferably Is from 505 nm to 550 nm. Of the two or more triplet luminescent complexes, the maximum peak wavelength of the emission spectrum of the triplet luminescent complex having the maximum peak wavelength of the emission spectrum on the longest wavelength side is preferably 570 nm or more and 680 nm or less. Preferably they are 590 nm or more and 630 nm or less.

  In order to adjust the luminescent color of a light-emitting device containing the metal complex of the present invention and the two or more triplet light-emitting complexes to white, the total content of the two or more triplet light-emitting complexes is When the content of the metal complex is 100 parts by weight, it is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 30 parts by weight, still more preferably 0.1 to 10 parts by weight. Particularly preferred is 0.5 to 5 parts by weight.

  When the maximum peak wavelength of the emission spectrum of the metal complex of the present invention is different from the maximum peak wavelength of the emission spectrum of the two or more triplet emission complexes, the emission color of the light-emitting element containing the metal complex of the present invention is white. In order to adjust, among the two or more triplet light emitting complexes, the content of the triplet light emitting complex having the maximum peak wavelength of the emission spectrum on the longest wavelength side is the shortest wavelength of the maximum peak wavelength of the emission spectrum. When the triplet light emitting complex on the side is 100 parts by weight, it is usually 1 to 10000 parts by weight, and preferably 5 to 1000 parts by weight because the color reproducibility of the light emitting device containing the metal complex of the present invention is excellent. More preferably, it is 10 to 200 parts by weight.

  The triplet light-emitting complex which may be contained in the light-emitting device of the present invention in combination with the metal complex of the present invention is preferably a triplet light-emitting complex (phosphorescent compound represented by the following formula (GR)) ).

[Where:
M represents a ruthenium atom, a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n ³ represents an integer of 1 or more, n ⁴ represents an integer of 0 or more, and n ³ + n ⁴ is 2 or 3. When M is a ruthenium atom, rhodium atom or iridium atom, n ³ + n ⁴ is 3, and when M is a palladium atom or platinum atom, n ³ + n ⁴ is 2.
E ⁴ represents a carbon atom or a nitrogen atom.
Ring R ³ represents a 6-membered aromatic heterocycle, and this ring R ³ may have a substituent. When a plurality of such substituents are present, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which each is bonded. When there are a plurality of rings R ³ , they may be the same or different.
Ring R ⁴ represents a 5-membered or 6-membered aromatic hydrocarbon ring, or a 5-membered or 6-membered aromatic heterocycle, and ring R ⁴ may have a substituent. When a plurality of such substituents are present, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which each is bonded. When a plurality of rings R ⁴ are present, they may be the same or different. However, when the ring R ⁴ is a 6-membered aromatic heterocycle, E ⁴ is a carbon atom.
The substituent that the ring R ³ may have and the substituent that the ring R ⁴ may have may be bonded to each other to form a ring together with the atoms to which they are bonded.
A ¹ -G ¹ -A ² represents an anionic bidentate ligand. A ¹ and A ² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. G ¹ represents a single bond or an atomic group constituting a bidentate ligand together with A ¹ and A ² . When a plurality of A ¹ -G ¹ -A ² are present, they may be the same or different. ]

E ⁴ is preferably a carbon atom.

When M is a ruthenium atom, rhodium atom or iridium atom, n ³ is preferably 2 or 3, and more preferably 3.

When M is a palladium atom or a platinum atom, n ³ is preferably 2.

Ring R ³ is a 6-membered aromatic heterocyclic ring, but the substituents of ring R ³ may be bonded to each other to form a ring with the atoms to which they are bonded. Ring R ³ is preferably a 6-membered aromatic heterocyclic ring having 1 to 4 nitrogen atoms as constituent atoms, and preferably 6-membered having 1 to 2 nitrogen atoms as constituent atoms. It is more preferably an aromatic heterocyclic ring, more preferably a pyridine ring, a diazabenzene ring, a quinoline ring or an isoquinoline ring, particularly preferably a pyridine ring, a quinoline ring or an isoquinoline ring, and these rings have a substituent. You may have.

Ring R ⁴ is a 5-membered or 6-membered aromatic hydrocarbon ring, or a 5-membered or 6-membered aromatic heterocycle, and the substituents of ring R ⁴ are bonded to each other. , And may form a ring together with the atoms to which each is bonded. The ring R ⁴ is preferably a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, pyridine ring, diazabenzene ring, pyrrole ring, furan ring or thiophene ring, and preferably a benzene ring, naphthalene ring or fluorene ring. More preferably, it is a benzene ring, and these rings may have a substituent.

Examples of the substituent that the ring R ³ and the ring R ⁴ may have include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a halogen atom, and a dendron Are preferred, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron is more preferred, an alkyl group, an aryl group or a dendron is more preferred, and these groups may further have a substituent. . When there are a plurality of substituents that the ring R ³ and the ring R ⁴ may have, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which they are bonded. .

In the formula (GR), the definition and examples of the anionic bidentate ligand represented by A ¹ -G ¹ -A ² are A ¹ -G ¹ in the metal complex represented by the above formula (1). represented by -A ² is the same as the definitions and examples of anionic bidentate ligand. However, the anionic bidentate ligand represented by A ¹ -G ¹ -A ² is different from the ligand whose number is defined by the subscript n ³ .

  The triplet light-emitting complex represented by the formula (GR) is preferably a phosphorescent compound represented by the formula (GR-A1) to the formula (GR-A5), and includes the formula (GR-A1) and the formula ( A triplet light-emitting complex represented by GR-A2) or formula (GR-A5) is more preferable.

[Where:
M ¹ , A ¹ -G ¹ -A ² , n ³ and n ⁴ represent the same meaning as described above.
R ^1C , R ^2C , R ^3C , R ^4C , R ^5C , R ^6C , R ^7C and R ^8C are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryl An oxy group, a monovalent heterocyclic group, a halogen atom or a dendron is represented, and these groups may have a substituent. When a plurality of R ^1C , R ^2C , R ^3C , R ^4C , R ^5C , R ^6C , R ^7C and R ^8C are present, they may be the same or different. R ^1C and R ^2C , R ^2C and R ^3C , R ^3C and R ^4C , R ^4C and R ^5C , R ^5C and R ^6C , R ^6C and R ^7C , and R ^7C and R ^8C are bonded to each other, You may form the ring with the carbon atom to which each couple | bonds. ]

R ^1C , R ^2C , R ^3C , R ^4C , R ^5C , R ^6C , R ^7C and R ^8C are a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, monovalent heterocyclic ring It is preferably a group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, and these groups may have a substituent.

  The dendron is preferably a group represented by the formula (D-A1), formula (D-A3), formula (D-B1) or formula (D-B3), and is represented by the formula (D-A1) or formula A group represented by (D-A3) is more preferable.

R ^1C , R ^4C , R ^5C and R ^8C are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group or a cycloalkoxy group, and a hydrogen atom, an alkyl group Alternatively, an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable. These groups may have a substituent.

R ^2C , R ^3C , R ^6C and R ^7C are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a dendron, It is more preferably an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, and further preferably a hydrogen atom or a dendron, and these groups may have a substituent.

It is preferred that at least one selected from the group consisting of R ^2C , R ^3C , R ^6C and R ^7C is a dendron, and more preferred that R ^2C or R ^6C is a dendron.

  Examples of the triplet light-emitting complex represented by the formula (GR-A1) are represented by the following formulas (GR-A1-1) to (GR-A1-24) shown in the following Tables 4 to 6. Triplet light-emitting complexes.

  The triplet light-emitting complex represented by the formula (GR-A2) is specifically a metal complex represented by the following formula (GR-A2).

[Where:
M ¹ , A ¹ -G ¹ -A ² , n ³ and n ⁴ represent the same meaning as described above.
R ^9C , R ^10C , R ^11C , R ^12C , R ^13C , R ^14C , R ^15C , R ^16C , R ^17C and R ^18C are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy Represents a group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups optionally have a substituent. When there are a plurality of R ^9C , R ^10C , R ^11C , R ^12C , R ^13C , R ^14C , R ^15C , R ^16C , R ^17C and R ^18C , they may be the same or different. R ^9C and R ^10C , R ^10C and R ^11C , R ^11C and R ^12C , R ^12C and R ^13C , R ^13C and R ^14C , R ^14C and R ^15C , R ^15C and R ^16C , R ^16C and R ^17C , and R ^17C and R ^18C may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]

R ^9C , R ^10C , R ^11C , R ^12C , R ^13C , R ^14C , R ^15C , R ^16C , R ^17C and R ^18C are a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group It is preferably a monovalent heterocyclic group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, and these groups have a substituent. Also good.

  The dendron is preferably a group represented by the formula (D-A1), formula (D-A3), formula (D-B1) or formula (D-B3), and is represented by the formula (D-A1) or formula A group represented by (D-B1) is more preferred, and a group represented by formula (D-A1) is more preferred.

R ^9C , R ^14C , R ^15C and R ^18C are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group or a cycloalkoxy group, and a hydrogen atom, an alkyl group Alternatively, an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable. These groups may have a substituent.

R ^11C , R ^12C and R ^13C are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a dendron, and a hydrogen atom, an alkyl group, It is more preferably an aryl group, a monovalent heterocyclic group or a dendron, further preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom, and these groups have a substituent. Also good.

R ^10C , R ^16C and R ^17C are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a dendron, and a hydrogen atom, an alkyl group, An aryl group, a monovalent heterocyclic group or a dendron is more preferable, and a hydrogen atom or a dendron is more preferable, and these groups may have a substituent.

Preferably, at least one selected from the group consisting of R ^{10C to} R ^13C , R ^16C and R ^17C is a dendron, more preferably R ^16C or R ^17C is a dendron, and R ^16C is further a dendron. preferable.

  Examples of the triplet light-emitting complex represented by the formula (GR-A2) include triplets represented by the following formulas (GR-A2-1) to (GR-A2-8) shown in Table 7 below. A luminescent complex is mentioned.

  The triplet light-emitting complex represented by the formula (GR-A3) is specifically a metal complex represented by the following formula (GR-A3).

[Wherein M ¹ , A ¹ -G ¹ -A ² , n ³ , n ⁴ , R ^9C , R ^10C , R ^11C , R ^12C , R ^13C , R ^14C , R ^15C , R ^16C , R ^17C and R ^18C represents the same meaning as described above. ]

  Examples of the triplet light-emitting complex represented by the formula (GR-A3) include triplets represented by the following formula (GR-A3-1) to the following formula (GR-A3-8) shown in the following Table 8. A luminescent complex is mentioned.

  The triplet light-emitting complex represented by the formula (GR-A4) is specifically a metal complex represented by the following formula (GR-A4).

[Wherein M ¹ , A ¹ -G ¹ -A ² , n ³ , n ⁴ , R ^9C , R ^10C , R ^11C , R ^12C , R ^13C , R ^14C , R ^15C , R ^16C , R ^17C and R ^18C represents the same meaning as described above. ]

  Examples of the triplet light-emitting complex represented by the formula (GR-A4) include triplets represented by the following formula (GR-A4-1) to the following formula (GR-A4-8) shown in the following Table 9. A luminescent complex is mentioned.

  The triplet light-emitting complex represented by the formula (GR-A5) is specifically a metal complex represented by the following formula (GR-A5).

[Where:
^{M 1, R 1C, R 2C} , R 3C, R 4C, R 5C, R 6C, R 7C, R 8C, R 9C, R 10C, R 11C, R 12C, R 13C, R 14C, R 15C, R 16C , R ^17C and R ^18C represent the same meaning as described above.
n ^3A and n ^4A each independently represents an integer of 1 or more, and n ^3A + n ^4A is 2 or 3. When M ¹ is an iridium atom, n ^3A + n ^4A is 3, and when M ¹ is a platinum atom, n ^3A + n ^4A is 2. ]

Examples of the triplet light-emitting complex represented by the formula (GR-A5) include triplets represented by the following formula (GR-A5-1) to the following formula (GR-A5-11) shown in the following Table 10. A luminescent complex is mentioned. In the formulas (GR-A5-1) to (GR-A5-11), R ^1C , R ^4C , R ^5C , R ^{8C to} R ^15C and R ^18C in the formula (GR-A5) represent a hydrogen atom. .

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

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

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

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

<Membrane>
The composition containing the metal complex of the present invention can be in the form of a film (layer).

  The film containing the metal complex (composition) of the present invention also includes an insolubilized film obtained by insolubilizing the metal complex of the present invention or other components in a solvent by crosslinking. The insolubilized film is a film obtained by crosslinking the metal complex of the present invention or other components by external stimulation such as heating or light irradiation. Since the insolubilized film is substantially insoluble in a solvent, further multilayering and thus high performance can be achieved without impairing the function and characteristics of the light emitting element.

  The heating temperature for crosslinking is usually 25 to 300 ° C., and since external quantum efficiency can be further improved, it is preferably 50 to 250 ° C., more preferably 150 to 200 ° C.

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

  The film containing the metal complex of the present invention is suitable as a light emitting layer, a hole transport layer, or a hole injection layer in a light emitting element.

  The film containing the metal complex of the present invention is formed using an ink, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method. , Spray coating, screen printing, flexographic printing, offset printing, ink jet printing, capillary coating, nozzle coating, and other coating methods.

  The thickness of the film containing the metal complex of the present invention is usually 1 nm to 10 μm.

<Light emitting element>
The light emitting device of the present invention is a light emitting device containing the metal complex of the present invention. The metal complex of the present invention contained in the light-emitting element may be crosslinked within a molecule or between molecules, and the metal complex of the present invention may be crosslinked within a molecule or between molecules.
As a structure of the light emitting element of this invention, the structure which has the electrode which consists of an anode and a cathode, and the layer containing the metal complex of this invention provided between this electrode is mentioned, for example.

[Layer structure]
The layer containing the metal complex of the present invention is usually a light emitting layer, a hole transport layer, a hole injection layer, and one or more layers selected from an electron transport layer and an electron injection layer, preferably a light emitting layer. is there. Each of these layers includes a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material.
Each of these layers uses a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material prepared by dissolving the electron injection material in the above-described solvent, and using the above-described coating method. Can be formed.

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

  Examples of the material for the hole transport layer, the electron transport layer, the light emitting layer, the hole injection layer, and the electron injection layer include the above-described hole transport material, electron transport material, and light emitting material, in addition to the metal complex of the present invention. , Hole injection materials and electron injection materials.

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

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

  The order, number and thickness of the layers to be stacked may be set in consideration of the external quantum efficiency and the luminance lifetime.

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

  Examples of the material of the anode among the electrodes include conductive metal oxides and translucent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium. Examples thereof include conductive compounds such as zinc oxide (IZO); composites of silver, palladium, and copper (APC); NESA, gold, platinum, silver, and copper.

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

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

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In this embodiment, room temperature means a temperature in the range of 25 ± 5 ° C.

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

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

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

NMR measurement was performed by the following method.
5 to 10 mg of a measurement sample was dissolved in about 0.5 mL of deuterated chloroform (CDCl ₃ -d ₁ ), deuterated tetrahydrofuran (THF-d ₈ ) or deuterated acetone ((CD ₃ ) ₂ CO-d ₆ ), and an NMR apparatus (Varian, Inc., product name: MERCURY 300), NMR device (manufactured by JEOL, product name: JNM-ECX400), or NMR device (manufactured by Bruker Corporation, product name: Avance III 600). And measured.

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

<Synthesis Example M1> Synthesis of Metal Complex CB1 First, Compound L1 was obtained using Compound L1-a and Compound L1-b according to the following scheme.

  Compound L1-a was synthesized according to the method described in US Patent Application Publication No. 2011/0057559.

  After making the inside of the reaction vessel an argon gas atmosphere, compound L1-a (9.9 g), compound L1-b (15 g), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (0.11 g), tris (Dibenzylideneacetone) dipalladium (0.12 g), 20 wt% tetraethylammonium aqueous solution (20 mL), toluene (200 mL) and ethanol (50 mL) were added, and the mixture was stirred for 18 hours under heating to reflux. Then, it cooled to room temperature and added toluene and extracted, and the organic layer was obtained. The obtained organic layer was washed with ion-exchanged water, and then concentrated under reduced pressure to obtain a solid. The obtained solid was purified by silica gel chromatography (eluent: mixed solvent of ethyl acetate and hexane), recrystallized using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure to give compound L1 ( 17 g, yield 90%).

  Compound CB1 was obtained from Compound L1 according to the following scheme.

  After the inside of the reaction vessel was filled with an argon gas atmosphere, Compound L1 (10 g), iridium chloride hydrate (2.2 g), 2-ethoxyethanol (120 mL) and water (40 mL) were added, and the mixture was stirred for 14 hours with heating under reflux. did. Then, when it cooled to room temperature and methanol was added, precipitation occurred. The resulting precipitate was filtered to obtain a solid. The obtained solid was washed with methanol and then dried under reduced pressure to obtain Compound CB1-a (10 g, yellow powder).

After the inside of the reaction vessel was filled with an argon gas atmosphere, compound CB1-a (9.5 g), silver trifluoromethanesulfonate (31 g), dichloromethane (100 mL) and methanol (30 mL) were added, and the mixture was stirred overnight at room temperature. After the deposited precipitate was filtered, the obtained filtrate was concentrated under reduced pressure. Thereafter, compound L1 (7.8 g), 2,6-lutidine (6.7 mL) and diethylene glycol dimethyl ether (180 mL) were added thereto, and the mixture was stirred overnight under heating to reflux. Then, it cooled to room temperature, the mixed solvent of ion-exchange water and methanol was added, the depositing deposit was filtered, and solid was obtained. The obtained solid was purified by silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane), recrystallized using a mixed solvent of toluene and acetonitrile, and then dried under reduced pressure to obtain metal complex CB1 ( 1.2 g, yield 6.5%). The result of ¹ H-NMR is as follows.

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

<Synthesis Example M2> Synthesis of Compound S1 Compound S1 was obtained according to the following scheme.

<Stage1>
After the inside of the reaction vessel was placed in a nitrogen gas stream, 4-tert-octylphenol (250.00 g, 1.21 mol, manufactured by Aldrich), N, N-dimethyl-4-aminopyridine (177.64 g, 1.45 mol) and Dichloromethane (3100 mL) was added and this was ice-cooled to 5 ° C. Thereafter, trifluoromethanesulfonic anhydride (376.06 g, 1.33 mol) was added dropwise thereto over 45 minutes. After completion of the dropwise addition, the mixture was stirred for 30 minutes under ice cooling, then returned to room temperature and further stirred for 1.5 hours to obtain a reaction mixture. Hexane (3100 mL) was added to the resulting reaction mixture, and the reaction mixture was filtered using 410 g of silica gel to obtain a filtrate. Further, a mixed solvent of hexane / dichloromethane (1/1 (volume basis)) ( 2.5L), the silica gel used for filtration was washed to obtain a washing solution. The obtained filtrate and washing solution were concentrated to obtain colorless oily compound S1-a (410.94 g, 1.21 mol, LC purity 99.7%).

<Stage2>
After the inside of the reaction vessel was placed in a nitrogen gas stream, compound S1-a (410.94 g, 1.21 mol), bis (pinacolato) diboron (338.47 g, 1.33 mol), potassium acetate (237.83 g, 2. 42 mol), 1,4-dioxane (2600 mL), palladium acetate (4.08 g, 0.018 mol) and tricyclohexylphosphine (10.19 g, 0.036 mol) were added and refluxed for 2 hours. After cooling to room temperature, the resulting reaction mixture was filtered to collect the filtrate, and the filtrate was further washed with 1,4-dioxane (2.5 L), and the obtained filtrate and washing were concentrated. The residue obtained by this concentration was dissolved in a mixed solvent of hexane / dichloromethane (1/1 (volume basis)) and filtered using 770 g of silica gel to obtain a filtrate. Further, hexane / dichloromethane (1 / The silica gel used for filtration was washed with a mixed solvent (2.5 L) of 1 (volume basis) to obtain a washing liquid. The obtained filtrate and washing liquid were concentrated, methanol (1500 mL) was added to the obtained residue, and ultrasonic washing was performed for 30 minutes. Then, the compound S1-b (274.27g) was obtained by filtering the obtained mixture. The filtrate and the washing solution were concentrated, methanol was added to the obtained residue, ultrasonic washing was performed, and filtration was repeated to obtain Compound S1-b (14.29 g). The total yield of the obtained compound S1-b was 288.56 g.

<Stage3>
After the inside of the reaction vessel was under a nitrogen gas stream, 1,3-dibromobenzene (102.48 g, 0.434 mol), compound S1-b (288.56 g, 0.912 mol), toluene (2100 mL), 20% by weight Tetraethylammonium hydroxide aqueous solution (962.38 g, 1.31 mol) and bis (triphenylphosphine) palladium (II) dichloride (3.04 g, 0.004 mol) were added and refluxed for 7 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the (first) organic layer was collected. Toluene (1 L) was added to this aqueous layer, and the (second) organic layer was further extracted. The obtained (first and second) organic layers were combined and washed with a mixed aqueous solution of distilled water / saturated saline (1.5 L / 1.5 L). The obtained organic layer was filtered through 400 g of silica gel to obtain a filtrate, and the silica gel used for filtration was further washed with toluene (2 L) to obtain a washing liquid. The obtained filtrate and washing solution were concentrated, and the obtained residue was dissolved in hexane to obtain a solution. This solution was purified by silica gel column chromatography. Impurities were eluted with hexane as a developing solvent, and then developed with a mixed solvent of hexane / dichloromethane (10/1 (volume basis)). The obtained fractions were concentrated under reduced pressure to remove the solvent, and colorless crystals of compound S1-c (154.08 g, LC purity 99.1%) and crude compound S1-c (38.64 g, LC purity 83) were obtained. %). This crude compound S1-c was purified again by column under the same development conditions as above, and the solvent was distilled off under reduced pressure to obtain compound S1-c (28.4 g, LC purity 99.6%). The total yield of the obtained compound S1-c was 182.48 g (0.40 mol).

<Stage4>
After the inside of the reaction vessel was under a nitrogen gas stream, compound S1-c (182, 48 g, 0.401 mol), bis (pinacolato) diboron (112.09 g, 0.441 mol), 4,4′-di-tert- Butyl-2,2′-dipyridyl (3.23 g, 0.012 mol), cyclohexane (2000 mL) and bis (1,5-cyclooctadiene) di-μ-methoxydiiridium (I) (3.99 g, 0.002 g). 006 mol) and refluxed for 2 hours. After air cooling to room temperature, silica gel (220 g) was added over 20 minutes while stirring the resulting reaction mixture. The obtained suspension was filtered through 440 g of silica gel, the silica gel was further washed with dichloromethane (2 L), and the solution was concentrated. Methanol (1100 mL) and dichloromethane (110 mL) were added to the obtained residue, and the mixture was refluxed for 1 hour. After cooling to room temperature, this was filtered. The obtained filtrate was washed with methanol (500 mL), and the obtained solid was dried to obtain compound S1 (220.85 g, 0.380 mol). The result of ¹ H-NMR is as follows.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 8.00 (d, J = 1.8 Hz, 2H), 7.92 (t, J = 1.9 Hz, 1H), 7.60 ( d, J = 8.5 Hz, 4H), 7.44 (t, J = 8.5 Hz, 4H), 1.78 (s, 4H), 1.41 (s, 12H), 1.37 (s, 12H), 0.75 (s, 18H).

<Synthesis Example M3> Synthesis of Triplet Luminescent Complex G1 Compound G1 was obtained from compound G1-a according to the following scheme.

<Stage1>
After making the inside of the reaction vessel an argon gas atmosphere, compound G1-a (36.17 g), compound S1 (94.20 g), toluene (1545 mL), 20 weight synthesized according to the method described in JP 2008-179617 A % Tetraethylammonium hydroxide aqueous solution (341.28 g) and tetrakis (triphenylphosphine) palladium (0) (8.927 g) were added, and the mixture was stirred at 80 ° C. for 4 hours. Water (1545 mL) was added to the obtained reaction liquid after cooling to room temperature, and the organic layer was extracted. The obtained organic layer was washed twice with water (1545 mL) and once with brine (1545 mL). The obtained organic layer was filtered using 188 g of silica gel, and the obtained filtrate was concentrated under reduced pressure. Toluene (235 g) and methanol (1174 g) were added to the obtained residue, and the mixture was heated at 60 ° C. for 30 minutes. Thereafter, this was cooled to 5 ° C. in an ice bath to precipitate a solid. The resulting solid was filtered and washed with cold methanol. The obtained solid was dried under reduced pressure to obtain compound G1-b (82.0 g) represented by the above formula G1-b.

<Stage2>
After making the inside of the reaction vessel a nitrogen gas atmosphere, iridium chloride trihydrate (11.51 g) and ion-exchanged water (114 mL) were added and heated to 50 ° C. to dissolve. Compound G1-b (43.80 g), 2-ethoxyethanol (792 mL) and ion-exchanged water (57 mL) were added to another reaction vessel in which the atmosphere in the vessel was a nitrogen gas atmosphere, and heated and stirred at 100 ° C. for 1 hour did. Thereafter, the previously prepared iridium chloride aqueous solution (total amount) was slowly dropped into this solution. After completion of dropping, the mixture was stirred at 120 ° C. for 15 hours. After cooling to room temperature, methanol (207 g) was added to the resulting reaction mixture and filtered to obtain a solid. The resulting solid was washed 4 times with methanol (207 g) and once with hexane (115 g). The obtained solid was dried under reduced pressure to obtain an intermediate (42.88 g) of compound G1.

After the inside of the reaction vessel was filled with nitrogen gas, compound G1 intermediate (7.61 g), compound G1-b (16.05 g), silver trifluoromethanesulfonate (1.63 g) and diethylene glycol dimethyl ether (79 mL) were added. , And stirred at 160 ° C. for 16 hours. After cooling to room temperature, methanol (304 mL) was added to the resulting reaction mixture, and the resulting precipitate was filtered. The precipitate obtained by filtration was purified by silica gel column chromatography (a mixed solvent of hexane / toluene = 4 / 6.5 (volume basis)), and the solvent was removed under reduced pressure. The obtained residue (8.05 g) was dissolved in dichloromethane (80 mL), and methanol (80 mL) was added to this solution. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain Compound G1 (6.25 g). The result of ¹ H-NMR is as follows.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz): δ (ppm) = 8.09 (m, 3H), 8.01 (s, 6H), 7.84 (m, 3H), 7.72 (d , 3H), 7.57 (m, 6H), 7.42 (d, 12H), 7.19 (d, 12H), 7.03 (d, 3H), 6.96-6.86 (m, 6H), 1.65 (s, 12H), 1.24 (s, 36H), 0.63 (s, 54H).

  <Synthesis Example M4> Synthesis of Triplet Luminescent Complex G2

  The triplet light emission complex G2 represented by the above formula G2 was synthesized according to the method described in JP-A-2006-188673.

  <Synthesis Example M5> Synthesis of Triplet Luminescent Complex R1

  The triplet light-emitting complex R1 represented by the formula R1 was synthesized according to the method described in JP-A-2008-179617.

  <Synthesis Example M6> Synthesis of Triplet Luminescent Complex R2

  The triplet light-emitting complex R2 represented by the formula R2 was synthesized according to the method described in JP2011-105701A.

  <Synthesis Example M7> Synthesis of Triplet Luminescent Complex R3

  The triplet light emitting complex R3 represented by the above formula R3 was synthesized according to the method described in JP-A-2006-188673.

<Example 1> Synthesis of Compound (B1) Compound (B1) (facial body) represented by the following formula B1 was synthesized according to a scheme including steps (1) to (6-1) below (in addition, The compound of Example 2 described later (
The process (6-2) for the synthesis of B2) (meridional form) is also shown. ).

Process (1)
3-Bromo-4-fluorobenzoyl chloride (13.4 g, 56.5 mmol) and pyridine (11.5 g, 154 mmol) were placed in a three-necked flask, and 2,6-dimethylaniline (6.20 g, 51.2 mmol) was placed in the three-necked flask. Was added dropwise and stirred for 16 hours under an argon gas atmosphere. After completion of the reaction, the reaction solution was distilled off under reduced pressure to obtain a solid. The obtained solid was poured into water and collected by filtration under reduced pressure to obtain 14.8 g of compound (B1-A) in a yield of 99%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 8.14 (dd, 1H), 7.83-7.93 (m, 1H), 7.30 (s, 1H), 7.10 -7.25 (m, 4H), 2.27 (s, 6H).

Step (2)
6.87 g (21.3 mmol) of compound (B1-A) and 4.39 g (21.4 mmol) of phosphorus pentachloride were placed in a three-necked flask, and then 60 mL of phosphoryl chloride was dropped into the three-necked flask under an argon gas atmosphere. Heated to reflux for 16 hours. After cooling to room temperature, phosphoryl chloride was distilled off under reduced pressure. To this, 60 mL of 2-propanol was added, and 44.0 g (0.42 mol) of aminoacetaldehyde dimethyl acetal was further added dropwise. After stirring for 16 hours, 12M hydrochloric acid was added dropwise and heated to reflux for 16 hours. After completion of the reaction, the precipitated black solid was filtered off to obtain a filtrate. A sodium hydroxide aqueous solution was added to the obtained filtrate to adjust the pH to about 9, and toluene was added for extraction to recover a black oily product. This product was separated and purified using silica gel chromatography (eluent: mixed solvent of ethyl acetate and dichloromethane) to obtain 4.73 g of compound (B1-B) in a yield of 64%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.74 (dd, 1H), 7.28-7.32 (m, 2H), 7.17 (d, 2H), 7.13 -7.16 (m, 1H), 6.88-6.93 (m, 2H), 1.97 (s.6H).

Process (3)
Compound (B1-B) 4.93 g (14.3 mmol), compound (B1-G) 8.04 g (17.2 mmol), triphenylphosphine 0.76 g (2.86 mmol), toluene 30 mL, ethanol 15 mL, 2M 30 mL of an aqueous sodium carbonate solution was placed in a three-necked flask, and argon gas was passed through for 15 minutes. Then, 0.52 g (0.72 mmol) of bis (triphenylphosphine) palladium (II) dichloride was added, and the mixture was heated to reflux for 16 hours under an argon gas atmosphere did. After cooling to room temperature, toluene was added for extraction, and the oil layer was recovered. The oil layer was concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of ethyl acetate and dichloromethane) to obtain 8.68 g of compound (B1-C) in a yield of 99%. Obtained. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / acetone-d ₆ ): δ (ppm) = 7.86 (t, 1H), 7.74-7.80 (m, 1H), 7.69 (dt, 4H), 7 .60 (dt, 4H), 7.44 (t, 1H), 7.36 (dd, 2H), 7.28 (d, 1H), 7.21-7.27 (m, 2H), 7. 14-7.20 (m, 2H), 2.08 (s, 6H), 1.37 (s, 18H).

Step (4)
400 mg (1.14 mmol) of iridium chloride n-hydrate, 1.51 g (2.49 mmol) of compound (B1-C), 36 mL of 2-ethoxyethanol, and 18 mL of water were placed in a three-necked flask, and the mixture was stirred for 16 hours under an argon gas atmosphere. Heated to reflux. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. 20 mL of water was added thereto, and the precipitated yellow solid was filtered off and washed with water and methanol to obtain 1.66 g of compound (B1-D) as a yellow powder. The obtained compound (B1-D) was used without further purification.

Process (5)
1.65 g (0.573 mmol) of compound (B1-D), 309 mg (1.20 mmol) of silver trifluoromethanesulfonate, 60 mL of dichloromethane, and 60 mL of methanol were placed in a three-necked flask and heated to reflux for 21.5 hours under an argon gas atmosphere. did. After cooling to room temperature, the solvent was distilled off under reduced pressure, 700 mg (5.73 mmol) of sodium acetylacetonate and 100 mL of acetonitrile were added thereto, and the mixture was heated to reflux for 17 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and 100 mL of dichloromethane was added thereto for filtration. The filtrate was distilled off under reduced pressure, and the resulting solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 1.03 g of compound (B1-E), yield 60 %. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / acetone-d ₆ ): δ (ppm) = 7.70 (s, 2H), 7.60 (d, 8H), 7.55 (d, 8H), 7.31-7 .41 (m, 14H), 6.44 (d, 2H), 6.39 (d, 2H), 5.33 (s, 1H), 2.24 (s, 6H), 2.13 (s, 6H), 1.80 (s, 6H), 1.36 (s, 36H).

Step (6-1) (Synthesis of Facial Compound (B1))
Compound (B1-E) 500 mg (0.31 mmol), Compound (B1-C) 300 mg (0.49 mmol), and glycerin 10 mL were placed in a three-necked flask and heated at a temperature around 225 ° C. for 26 hours under an argon gas atmosphere. Reacted. The mixture was cooled to room temperature, 50 mL of methanol was added, and the generated solid was collected by filtration. Subsequently, the obtained solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 92 mg of a facial compound (B1) in a yield of 15%. The result of ¹ H-NMR is as follows.
¹ H-NMR (acetone-d ₆ ): δ (ppm) = 7.69 (s, 3H), 7.62 (d, 12H), 7.57 (d, 12H), 7.33-7.40 (M, 12H), 7.25 (s, 3H), 7.19 (t, 3H), 6.95 (s, 3H), 6.76 (d, 3H), 6.59 (d, 3H) 2.21 (s, 9H), 1.99 (s, 9H), 1.26 (s, 54H).

<Example 2> Synthesis of Meridional Compound (B2) Compound (B2) (meridional compound) represented by the following formula B2 is subjected to the following step from step (1) to step (5). Synthesized according to (6-2).

Step (6-2) (Synthesis of Meridional Compound (B2))
500 mg (0.31 mmol) of the compound (B1-E) obtained in the step (5) of Example 1, 300 mg (0.49 mmol) of the compound (B1-C) and 10 mL of ethylene glycol were put into a three-necked flask, and an argon gas atmosphere Under reflux for 3 hours. It cooled to room temperature, 50 mL of methanol was added, and it collect | recovered by filtering the produced | generated solid. Subsequently, the obtained solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 165 mg of a meridional compound (B2) in a yield of 26%. The result of ¹ H-NMR is as follows.
¹ H-NMR (acetone-d ₆ ): δ (ppm) = 7.68-7.71 (m, 3H), 7.55-7.64 (m, 24H), 7.18-7.43 ( m, 16H), 7.11 (s, 2H), 6.93-6.96 (m, 2H), 6.84 (d, 1H), 6.79 (s, 1H), 6.65-6. .72 (m, 3H), 6.57 (t, 2H), 2.22-2.25 (m, 9H), 2.06 (s, 3H), 1.97-1.99 (m, 6H) ), 1.38 (s, 54H).

Example 3 Synthesis of Compound (B3) A compound (B3) (facial body) represented by the following formula B3 was synthesized according to a scheme including the following steps (1) to (6).

Process (1)
3- (Trifluoromethyl) benzoyl chloride (7.79 g, 37.4 mmol), pyridine (3 mL), and chloroform (20 mL) were placed in a three-necked flask, and in an argon gas atmosphere, 4-bromo-2,6-dimethylaniline (6.76 g, 33.33 g) was added. 8 mmol) was added dropwise and stirred at room temperature for 16 hours. After completion of the reaction, the reaction solution was distilled off under reduced pressure to obtain a pale yellow solid. The obtained pale yellow solid was recrystallized using dichloromethane to obtain 10.2 g of Compound (B3-A) in a yield of 81%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 8.16 (s, 1H), 8.10 (d, 1H), 7.84 (d, 1H), 7.66 (t, 1H) ), 7.29 (s, 2H), 2.27 (s, 6H).

Step (2)
4.28 g (11.5 mmol) of compound (B3-A) and 2.40 g (11.5 mmol) of phosphorus pentachloride are placed in a three-necked flask, 5 mL of phosphoryl chloride is added dropwise, and the mixture is heated under an argon gas atmosphere for 5 hours. Refluxed. After cooling to room temperature, phosphoryl chloride was distilled off under reduced pressure. To this, 10 mL of 2-propanol was added, and 10.5 g (99.9 mmol) of aminoacetaldehyde dimethyl acetal was further added dropwise. After stirring for 5 hours, 12M hydrochloric acid was added dropwise and heated to reflux for 16 hours. After completion of the reaction, the precipitated black solid was filtered off and washed with water. This black solid was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain 3.43 g of compound (B3-B) in a yield of 75%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.83 (s, 1H), 7.52 (d, 1H), 7.35-7.43 (m, 5H), 6.93 (S, 1H), 1.94 (s, 6H).

Process (3)
Iridium chloride n-hydrate 1.11 g (3.15 mmol), compound (B3-B) 2.60 g (6.58 mmol), 2-ethoxyethanol 100 mL, and water 50 mL were placed in a three-necked flask under an argon gas atmosphere. Heated to reflux for 16 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. 50 mL of water was added thereto, and the precipitated yellow solid was filtered off and washed with water and methanol to obtain 3.20 g of compound (B3-C) as a yellow powder. This compound (B3-C) was used without further purification.

Process (4)
3.43 g (1.69 mmol) of the compound (B3-C), 920 mg (3.58 mmol) of silver trifluoromethanesulfonate, 80 mL of dichloromethane, and 80 mL of methanol were placed in a three-necked flask and heated to reflux for 17 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, 791 mg (6.48 mmol) of sodium acetylacetonate and 100 mL of acetonitrile were added thereto, and the mixture was heated to reflux for 18 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and 200 mL of dichloromethane was added and filtered. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and toluene) to obtain 2.47 g of compound (B3-D), yield. Obtained at 82%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.48 (s, 4H), 7.25 (s, 2H), 6.97 (s, 2H), 6.79 (d, 2H) ), 6.59 (d, 2H), 6.30 (s, 2H), 5.26 (s, 1H), 2.13 (s, 6H), 2.05 (s, 6H), 1.83 (S, 6H).

Process (5)
Compound (B3-D) 1.51 g (1.39 mmol), Compound (B3-B) 818 mg (2.07 mmol), and ethylene glycol 10 mL were placed in a three-necked flask and heated and reacted at 160 ° C. for 15 hours in an argon gas atmosphere. . After cooling to room temperature, 50 mL of water was added, and the generated solid was collected by filtration. Subsequently, the obtained solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane). 1.18 g of a facial compound (B3-E) was obtained in a yield of 62%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.43 (s, 6H), 6.82 (d, 6H), 6.79 (s, 3H), 6.72 (d, 3H ), 6.39 (d, 3H), 2.08 (s, 9H), 1.84 (s, 9H).

Step (6)
1.83 g (1.33 mmol) of the compound (B3-E), 2.83 g (6.04 mmol) of the compound (B3-G), 80 mL of toluene, 15 mL of ethanol, and 25 mL of 2M aqueous sodium carbonate solution were placed in a three-necked flask, and argon gas was added. Then, 0.486 g (0.42 mmol) of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated to reflux for 62 hours under an argon gas atmosphere. After cooling to room temperature, toluene was added for extraction, and the oil layer was recovered. The oil layer was concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 0.851 g of facial compound (B3), yield 30%. I got it. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / acetone-d ₆ ): δ (ppm) = 7.85 (d, 6H), 7.80 (dd, 9H), 7.66 (t, 12H), 7.45 (dt , 12H), 7.26 (d, 3H), 6.82-6.86 (m, 6H), 6.75 (dd, 3H), 6.43 (d, 3H), 2.17 (s, 9H), 1.87 (s, 9H), 1.26 (s, 54H).

<Example 4> Synthesis of Compound (B4) Compound (B4) (facial body) represented by the following formula B4 was synthesized according to a scheme including the following steps (1) to (6-1) (in addition, The process (6-2) for the synthesis of the compound (B5) (meridional form) of Example 5 described later is also shown.

Process (1)
4-Fluoro-3- (trifluoromethyl) benzoyl chloride (5.08 g, 22.4 mmol), pyridine (3 mL) and chloroform (20 mL) were placed in a three-necked flask, and 4-bromo-2,6-dimethylaniline was added under an argon gas atmosphere. 45 g (22.2 mmol) was added dropwise and stirred at room temperature for 16 hours. After completion of the reaction, the reaction solution was distilled off under reduced pressure to obtain a solid. This was recrystallized using dichloromethane and hexane to obtain 8.47 g of Compound (B4-A) in a yield of 98%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 8.18 (d, 1H), 8.12-8.15 (m, 1H), 7.35 (t, 1H), 7.29 (S, 2H), 2.25 (s, 6H).

Step (2)
Compound (B4-A) 3.54 g (9.07 mmol) and phosphorus pentachloride 1.71 g (8.23 mmol) were placed in a three-necked flask, 10 mL of phosphoryl chloride was added dropwise, and the mixture was heated to reflux for 5 hours under an argon gas atmosphere. did. After cooling to room temperature, phosphoryl chloride was distilled off under reduced pressure. To this was added 20 mL of 2-propanol, and 9.37 g (89.1 mmol) of aminoacetaldehyde dimethyl acetal was further added dropwise. After stirring for 5 hours, 15 mL of 12M hydrochloric acid was added dropwise and heated to reflux for 16 hours. After completion of the reaction, 10% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the precipitated solid was filtered off and washed with water. The obtained solid was separated and purified by silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 2.638 g of compound (B4-B) in a yield of 78%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.79 (d, 1H), 7.41 (m, 1H), 7.35 (m, 3H), 7.05 (t, 1H) ), 6.91 (s, 1H), 1.94 (s, 6H).

Step (3)
152 mg (0.43 mmol) of iridium chloride n-hydrate, 349 mg (0.84 mmol) of compound (B4-B), 14 mL of 2-ethoxyethanol, and 7 mL of water were placed in a three-necked flask and heated under reflux for 16 hours under an argon gas atmosphere. did. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. 7 mL of water was added thereto, and the precipitated yellow solid was filtered off and washed with water and methanol to obtain 401 mg of the compound (B4-C) as a yellow powder. Compound (B4-C) was used without further purification.

Process (4)
401 mg (0.19 mmol) of the compound (B4-C), 106.8 mg (0.42 mmol) of silver trifluoromethanesulfonate, 30 mL of dichloromethane, and 10 mL of methanol were placed in a three-necked flask and heated to reflux for 17 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, 96.2 mg (0.78 mmol) of sodium acetylacetonate and 30 mL of acetonitrile were added thereto, and the mixture was heated to reflux for 2 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and 100 mL of dichloromethane was added thereto for filtration. The filtrate was evaporated under reduced pressure, and the resulting brown solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane). As a yellow powder, 306 mg of the compound (B4-D) was obtained in a yield of 72%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.47 (d, 4H), 7.20 (d, 2H), 6.98 (d, 2H), 6.26 (d, 2H) ), 6.17 (d, 2H), 5.28 (s, 1H), 2.12 (s, 6H), 2.04 (s, 6H), 1.85 (s, 6H).

Process (5)
280 mg (0.25 mmol) of the compound (B4-D), 127 mg (0.31 mmol) of the compound (B4-B) and 15 mL of ethylene glycol were placed in a three-necked flask, and the reaction was performed by heating at 150 ° C. for 15 hours in an argon gas atmosphere. After cooling to room temperature, 50 mL of water was added, and the generated solid was collected by filtration. Subsequently, the obtained solid was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and hexane). As a result, a facial compound (B4-E) and a meridional compound (B4-E) were obtained. Were obtained respectively.

The yield of the facial compound (B4-E) was 55.2 mg, and the yield was 15%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.45 (s, 6H), 6.80 (d, 3H), 6.66 (d, 3H), 6.48 (d, 3H) ), 6.36 (d, 3H), 2.08 (s, 9H), 1.86 (s, 9H).

The yield of the meridional compound (B4-E) was 207 mg, and the yield was 58%.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.39-7.48 (m, 6H), 6.81 (s, 1H), 6.69-6.72 (m, 3H) 6.59-6.64 (m, 3H), 6.40-6.47 (m, 3H), 6.37 (t, 2H), 2.11 (s, 3H), 2.07 (d , 6H), 1.93 (s, 3H), 1.84 (d, 6H).

Step (6-1) (Synthesis of Facial Compound (B4))
1.60 g (1.12 mmol) of facial compound (B4-E), 1.69 g (3.62 mmol) of compound (B4-G), 40 mL of toluene, 15 mL of ethanol, and 20 mL of 2M aqueous sodium carbonate solution were placed in a three-necked flask. After argon gas was bubbled for 15 minutes, 0.2876 g (0.249 mmol) of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated to reflux for 13 hours under an argon gas atmosphere. After cooling to room temperature, toluene was added for extraction, and the oil layer was recovered. The oil layer was concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane). 1.39 g of a facial compound (B4) was obtained in a yield of 56%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.83 (s, 3H), 7.77 (s, 6H), 7.64 (d, 12H), 7.57 (d, 6H) ), 7.53 (d, 12H), 6.93 (s, 3H), 6.75 (s, 3H), 6.55 (d, 3H), 6.45 (d, 3H), 2.20 (S, 9H), 1.99 (s, 9H), 1.37 (s, 54H).

<Example 5> Synthesis of metal complex B5 A compound (B5) (meridional form) represented by the following formula B5 is subjected to the following step (6-2) following the step (1) to the step (5). ).

Step (6-2) (Synthesis of Meridional Compound (B5))
531 mg (0.371 mmol) of the meridional compound (B4-E) obtained in step (5) of Example 4, 548 mg (1.17 mmol) of compound (B4-G), 20 mL of toluene, 10 mL of 2M aqueous sodium carbonate solution Was put into a three-necked flask, and argon gas was bubbled through for 15 minutes. Then, 144 mg (0.125 mmol) of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated to reflux for 15 hours under an argon gas atmosphere. After cooling to room temperature, toluene was added for extraction, and the oil layer was recovered. The oil layer was concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 237 mg of a meridional compound (B5) in 29% yield. It was. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.82-7.84 (m, 3H), 7.76-7.78 (m, 6H), 7.63-7.68 ( m, 12H), 7.51-7.57 (m, 18H), 6.94 (s, 1H), 6.85 (m, 1H), 6.77-6.81 (m, 2H), 6 70-6.74 (m, 2H), 6.66-6.67 (m, 1H), 6.53-6.57 (m, 3H), 6.45-6.50 (m, 2H) , 2.24 (s, 3H), 2.19 (s, 6H), 2.06 (s, 3H), 1.97 (s, 6H), 1.39 (s, 54H).

Example 6 Synthesis of Compound (B6-F) A compound (B6-F) represented by the following formula (B6-F) was synthesized according to a scheme including the following steps (1) to (6).

Process (1)
4-Bromo-2,6-dimethylaniline 1.43 g (7.15 mmol), compound (B6-G) 4.03 g (8.60 mmol), triphenylphosphine 279 mg (1.06 mmol), K ₃ PO ₄ 6. 3991 g (30.1 mmol), 30 mL of toluene, 15 mL of ethanol, 15 mL of water, 10 mL of 2M aqueous sodium carbonate solution were placed in a three-necked flask and aerated with argon gas for 15 minutes, and then 508 mg (0.55 mmol) of tris (dibenzylideneacetone) dipalladium. ) And heated to reflux for 3 hours under an argon gas atmosphere. After cooling to room temperature, toluene was added for extraction, and the oil layer was recovered. The oil layer was concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and hexane) to obtain 2.53 g of compound (B6-A) in a yield of 76%. Obtained. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.69 (m, 3H), 7.61 (d, 4H), 7.50 (d, 4H), 7.29 (s, 2H) ), 3.67 (s, 2H), 2.26 (s, 6H), 1.38 (s, 18H).

Process (2)
2.00 g (9.12 mmol) of 3-bromobenzoyl chloride, 2 mL of pyridine, and 50 mL of dichloromethane are placed in a three-necked flask, and 3.31 g (7.17 mmol) of compound (B6-A) is added dropwise under an argon gas atmosphere at room temperature. Stir for 16 hours. After completion of the reaction, the reaction solution was distilled off under reduced pressure to obtain a solid. This was recrystallized from dichloromethane and hexane to obtain 3.91 g of Compound (B6-B) in a yield of 85%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 8.09 (s, 1H), 7.86 (d, 1H), 7.77 (s, 1H), 7.73-7.76 (M, 3H), 7.63 (d, 4H), 7.51 (s, 4H), 7.36-7.44 (s, 4H), 2.37 (s, 6H), 1.38 ( s, 18H).

Process (3)
After putting 2.49 g (3.86 mmol) of compound (B6-B) and 778 mg (3.74 mmol) of phosphorus pentachloride in a three-necked flask, 20 mL of phosphoryl chloride was added dropwise, and the mixture was heated to reflux for 5 hours under an argon gas atmosphere. . After cooling to room temperature, phosphoryl chloride was distilled off under reduced pressure. 2-propanol 40mL was added here, and also aminoacetaldehyde dimethyl acetal 7.82g (74.4 mmol) was dripped. After stirring for 7 hours, 20 mL of 12M hydrochloric acid was added dropwise and heated to reflux for 16 hours. After completion of the reaction, 2-propanol was distilled off under reduced pressure, 10% aqueous sodium hydroxide solution was added to adjust the pH to 11, and the product was recovered by extraction with dichloromethane. This product was separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate) to obtain 2.29 g of compound (B6-C) in a yield of 91%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.77-7.81 (m, 4H), 7.64 (d, 4H), 7.48-7.52 (m, 6H) 7.36-7.38 (m, 2H), 7.19 (d, 1H), 7.05 (t, 1H), 6.98 (s, 1H), 2.04 (s, 6H), 1.39 (s, 18H).

Process (4)
Compound (B6-C) 1.60 g (2.3 mmol), copper (I) cyanide 433 mg (4.9 mmol), N-methyl-2-pyrrolidone (NMP) 30 mL were added at 175 ° C. under argon gas atmosphere. The reaction was conducted by heating for a period of time. The reaction solution was cooled to room temperature, poured into 200 mL of water in which 1.02 g (20.9 mmol) of sodium cyanide was dissolved, and stirred at 50 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was extracted with dichloromethane, concentrated under reduced pressure, and the resulting solid was separated and purified using silica gel chromatography (eluent: mixed solvent of ethyl acetate and hexane) to give compound (B6-D ) Was obtained in a yield of 85%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / acetone-d ₆ ): δ (ppm) = 7.82 (d, 2H), 7.79 (t, 1H), 7.69-7.71 (m, 3H), 7 .64 (dd, 4H), 7.55 (t, 2H), 7.43 (dd, 4H), 7.35 (t, 1H), 7.22 (s, 1H), 7.19 (s, 1H), 1.94 (s, 6H), 1.25 (s, 18H).

Process (5)
80 mg (0.022 mmol) of iridium chloride n-hydrate, 27.3 mg (0.044 mmol) of compound (B6-D), 20 mL of 2-ethoxyethanol, and 10 mL of water were placed in a three-necked flask, and the mixture was stirred under an argon gas atmosphere for 16 hours. Heated to reflux. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. 10 mL of water was added thereto, the precipitated solid was separated by filtration, and washed with water and methanol to obtain 32.1 mg of compound (B6-E). This compound (B6-E) was used without further purification.

Step (6)
804 mg (0.28 mmol) of the compound (B6-E), 161.6 mg (0.63 mmol) of silver trifluoromethanesulfonate, 40 mL of dichloromethane, and 20 mL of methanol were placed in a three-necked flask and heated to reflux for 17 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, 138.1 mg (1.13 mmol) of sodium acetylacetonate and 30 mL of acetonitrile were added thereto, and the mixture was heated to reflux for 3 hours under an argon gas atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and 100 mL of dichloromethane was added thereto for filtration. The filtrate was evaporated under reduced pressure, and the resulting brown solid was separated and purified using silica gel column chromatography (eluent: dichloromethane) to obtain 285 mg of compound (B6-F) in a yield of 34%. The result of ¹ H-NMR is as follows.
¹ H-NMR (400 MHz / acetone-d ₆ ): δ (ppm) = 7.97-8.03 (m, 8H), 7.93 (s, 2H), 7.78 (d, 8H), 7 .57 (t, 10H), 7.37 (d, 2H), 6.84 (t, 2H), 6.76 (d, 2H), 6.40 (d, 2H), 5.34 (s, 1H), 2.29 (s, 6H), 2.20 (s, 6H), 1.80 (s, 6H), 1.38 (s, 36H).

<PL spectrum measurement>
The PL spectrum was measured by the following method.
A measurement sample was dissolved in xylene to a concentration of 8.0 × 10 ⁻⁴ wt% and sealed in a quartz cell, and a xenon lamp (Model E7536, manufactured by Hamamatsu Photonics) was used as an excitation light source. The measurement sample was excited at an excitation wavelength of 300 nm via Model A10080-02, manufactured by Hamamatsu Photonics. The PL spectrum was measured using a multi-channel spectrometer (manufactured by Hamamatsu Photonics, PMA12).

<PL spectrum of metal complex>
PL spectra of metal complexes (compounds) CB1, B1, B2, B3, B4, B5, G1, G2, R1, R2, and R3 were measured. Table 11 shows the emission peak wavelength (maximum peak wavelength) and CIE chromaticity coordinates (CIE-x, CIE-y) of each metal complex.

<Evaluation of color rendering properties>
The PL spectrum of the metal complex of the present invention, and the PL spectra of two types of triplet light emission complexes having a maximum peak wavelength of 495 nm or more and less than 750 nm, and white emission with a color temperature of 3500K, 4000K, or 5000K on the Plankian locus. The color rendering properties were evaluated by calculating the average color rendering index Ra from the spectrum obtained by adding together to obtain a spectrum by the method described in JIS Z8726-1990. It shows that color rendering property is so high that the value of obtained Ra is large.

<Comparative example 1> Average color rendering index Ra of metal complex CB1
A PL spectrum of the metal complex CB1, a PL spectrum of the metal complex G1 or G2, and one PL spectrum selected from the metal complexes R1, R2, and R3, a color temperature of 3500K, 4000K on the Plankian locus, or As described above, the average color rendering index Ra was calculated from the PL spectrum obtained by adding the white emission spectrum of 5000K. The results are shown in Table 12 below.

<Example 7> Average color rendering index Ra of metal complex B1
The average color rendering index Ra when the metal complex B1 was used was calculated in the same manner as in Comparative Example 1 except that the metal complex B1 was used instead of the metal complex CB1. The results are shown in Table 13 below.

<Example 8> Average color rendering index Ra of metal complex B2
The average color rendering index Ra when the metal complex B2 was used was calculated in the same manner as in Comparative Example 1 except that the metal complex B2 was used instead of the metal complex CB1. The results are shown in Table 14 below.

<Example 9> Average color rendering index Ra of metal complex B3
The average color rendering index Ra when the metal complex B3 was used was calculated in the same manner as in Comparative Example 1 except that the metal complex B3 was used instead of the metal complex CB1. The results are shown in Table 15 below.

<Example 10> Average color rendering index Ra of metal complex B4
The average color rendering index Ra when the metal complex B4 was used was calculated in the same manner as in Comparative Example 1 except that the metal complex B4 was used instead of the metal complex CB1. The results are shown in Table 16 below.

<Example 11> Average color rendering index Ra of metal complex B5
The average color rendering index Ra when the metal complex B5 was used was calculated in the same manner as in Comparative Example 1 except that the metal complex B5 was used instead of the metal complex CB1. The results are shown in Table 17 below.

  From these results, when the metal complex of the present invention is used, it is possible to realize a white luminescent color which is superior in color rendering as compared with the case where the metal complex CB1 is used.

Claims (10)

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

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

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

[Where:
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent. A plurality of ^GDA may be the same or different.
Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good. When there are a plurality of Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of ^TDAs may be the same or different. ] The metal complex according to claim 1, wherein any one of R ⁴ and R ⁵ is an alkyl group having a fluorine atom as a substituent. The metal complex according to claim 1, wherein at least one selected from the group consisting of R ⁴ and R ⁹ is a group represented by the formula (DA). The group represented by the said formula (DA) is group represented by following formula (D-A1), (D-A2), or (D-A3), The any one of Claims 1-3 The metal complex according to item.

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group or a halogen atom. When a plurality of R ^p1 and R ^p2 are present, they may be the same or different.
np1 represents an integer of 1 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]   The metal complex according to claim 4, wherein the group represented by the formula (DA) is a group represented by the formula (D-A1). The metal complex according to claim 1, wherein n ₂ is 1. The metal complex according to claim 1, wherein n ₁ is 3. 7. The metal complex according to any one of claims 1 to 7,
The composition containing the compound represented by a following formula (H-1).

[In the formula (H-1),
Ar ^H1 and Ar ^H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
n ^H1 and n ^H2 each independently represent 0 or 1. When a plurality of n ^H1 are present, they may be the same or different. When a plurality of n ^H2 are present, they may be the same or different.
n ^H3 represents an integer of 0 or more.
L ^H1 represents an arylene group, a divalent heterocyclic group, or a group represented by — [C (R ^H11 ) ₂ ] n ^H11 —, and these groups optionally have a substituent. When a plurality of L ^H1 are present, they may be the same or different.
n ^H11 represents an integer of 1 or more and 10 or less. R ^H11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^H11 may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
L ^H2 represents a group represented by -N (-L ^H21 -R ^H21 )-. When a plurality of L ^H2 are present, they may be the same or different.
L ^H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. R ^H21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ] 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 a solvent.   The light emitting element containing the metal complex of any one of Claims 1-7.