JP5294242B2 - Metal coordination compound and light emitting material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a metal coordination compound that is a light-emitting element material having high luminance and high efficiency, emitting a red light and having durability and is useful as a light-emitting element, a laser pigment etc. <P>SOLUTION: The metal coordination compound has a partial structure represented by general formula (1) (wherein M is indium or platinum; N is a nitrogen atom; and R<SP>1</SP>-R<SP>11</SP>are each independently a hydrogen atom or a substituent group, here, adjacent substituent groups may be bonded to form a cyclic structure). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an organic electroluminescent element material, an electrochemiluminescence (ECL) element material, a light emitting sensor, a photosensitizer, a display, a photographic material, a laser dye, a color filter dye, optical communication, a color conversion filter, a back The present invention relates to a metal coordination compound useful for light, illumination, photosensitizing dye, various light sources, and the like, and a light emitting material comprising the compound.

  Organic electroluminescent elements are attracting attention as next-generation display elements, and in recent years, various organic materials used in light-emitting elements have been actively developed. In particular, as a light-emitting material, attention has been focused on a phosphorescent material using light emission from an excited triplet state.

  In the case of using emission from an excited singlet state, the generation ratio of singlet excitons and triplet excitons is 1: 3, so that the generation probability of luminescent excited species is 25%, and the light extraction efficiency is high. Since it is about 20%, the limit of the external extraction quantum efficiency is set to 5%. On the other hand, if an excited triplet state can also be used for this, since the upper limit of the internal quantum efficiency is 100%, the emission efficiency is four times in principle compared to the case of an excited singlet. Development of organic electroluminescent elements using sucrose has been actively conducted. Among them, as a phosphorescent material, an orthometalated iridium complex represented by a tris (2-phenylpyridine) iridium complex is a compound that has attracted particular attention (Patent Document 1), but this phosphorescent material is limited to green light emission. Therefore, development of a new phosphorescent material is desired.

International Publication No. 00/70655 Pamphlet

  An object of the present invention is to provide a light-emitting element that can emit light with high luminance and high efficiency and has excellent durability, and can be used for the light-emitting element. Organic electroluminescent element material, electrochemiluminescence (ECL) element material, light-emitting sensor, light Providing novel metal coordination compounds that can be applied to sensitizers, displays, photographic materials, laser dyes, dyes for color filters, optical communications, color conversion filters, backlights, lighting, photosensitizing dyes, various light sources, etc. It is to be.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the novel metal coordination compound represented by the general formula (1) or (2) has excellent light emission characteristics in the visible light region (particularly the red region). It has been found that it is useful as a light emitting material for various uses, and the present invention has been completed.

（一般式（１）中、Ｍはイリジウムまたは白金を表す。Ｎは窒素原子を表す。Ｒ^１〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。）
〈２〉下記一般式（２）で表される金属配位化合物。

（一般式（２）中、Ｍはイリジウムまたは白金を表す。Ｎは窒素原子を表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎ＝２または３である。Ｒ^１〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。Ｑはカウンターアニオンを表す。ｋは０〜２の整数を表す。Ｌは２座配位子を表す。）
〈３〉Ｌは、Ｍ−窒素結合およびＭ−炭素結合を形成する２座配位子、Ｍ−窒素結合およびＭ−酸素結合を形成する２座配位子、Ｍ−酸素結合を２つ形成する２座配位子、または、Ｍ−窒素結合を２つ形成する２座配位子である前記２に記載の金属配位化合物。
〈４〉Ｌは、一般式（３）〜（８）の何れかで表される前記２または３に記載の金属配位化合物。

（一般式（３）〜（８）中、Ｒ^１２〜Ｒ^４７は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。）
〈５〉ｍ＝３かつｎ＝０である前記２に記載の金属配位化合物。
〈６〉ｍ＝２かつｎ＝１である前記２から４何れかに記載の金属配位化合物。
〈７〉Ｒ^１とＲ^２とが、炭素原子数３〜２０の飽和炭素環を形成していることを特徴とする前記１から６何れかに記載の金属配位化合物。
〈８〉Ｒ^１およびＲ^２が、各々独立に、炭素原子数１〜３０のアルキル基または炭素原子数１〜３０の置換アルキル基であることを特徴とする前記１から６何れかに記載の金属配位化合物。
〈９〉Ｒ^３からＲ^４７が、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、シアノ基、アミノ基、ヘテロ環基、アシル基、水酸基、または、トリフロオロメチル基から選ばれることを特徴とする前記１から８何れかに記載の金属配位化合物。
〈１０〉Ｒ^５およびＲ^１０が、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、シアノ基、アミノ基、ヘテロ環基、アシル基、水酸基、または、トリフロオロメチル基から選ばれることを特徴とする前記１から９何れかに記載の金属配位化合物。
〈１１〉Ｍがイリジウムである前記１から１０何れかに記載の金属配位化合物。
〈１２〉前記１から１１何れかに記載の金属配位化合物からなる発光材料。
〈１３〉前記１２に記載の発光材料を用いた発光素子。
〈１４〉一般式（９）で表される、前記１から１１何れかに記載の金属配位化合物の中間体。

（一般式（９）中、Ｍはイリジウムまたは白金を表す。Ｎは窒素原子を表す。Ｍがイリジウムのときはｍ^１＝２であり、Ｍが白金のときはｍ^１＝１である。Ｒ^１〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。Ｘはハロゲン原子を表す。） That is, according to this application, the following invention is provided.
<1> A metal coordination compound having a partial structure represented by the following general formula (1).

(In General Formula (1), M represents iridium or platinum. N represents a nitrogen atom. R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a substituent. Adjacent substituents are bonded. To form a ring structure.)
<2> A metal coordination compound represented by the following general formula (2).

(In General Formula (2), M represents iridium or platinum. N represents a nitrogen atom. M represents an integer of 1 to 3. n represents an integer of 0 to 2. m + n = 2 or 3. R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a substituent, and adjacent substituents may be bonded to form a ring structure, Q represents a counter anion, k represents 0 to 0 Represents an integer of 2. L represents a bidentate ligand.)
<3> L forms a bidentate ligand that forms an M-nitrogen bond and an M-carbon bond, a bidentate ligand that forms an M-nitrogen bond and an M-oxygen bond, and two M-oxygen bonds 3. The metal coordination compound according to 2 above, which is a bidentate ligand or a bidentate ligand that forms two M-nitrogen bonds.
<4> The metal coordination compound according to 2 or 3, wherein L is represented by any one of the general formulas (3) to (8).

(In the general formulas (3) to (8), R ^{12 to} R ⁴⁷ each independently represents a hydrogen atom or a substituent. Adjacent substituents may be bonded to form a ring structure. )
<5> The metal coordination compound according to 2 above, wherein m = 3 and n = 0.
<6> The metal coordination compound according to any one of 2 to 4, wherein m = 2 and n = 1.
<7> The metal coordination compound as described in any one of 1 to 6 above, wherein R ¹ and R ² form a saturated carbocyclic ring having 3 to 20 carbon atoms.
<8> R ¹ and R ² are each independently an alkyl group having 1 to 30 carbon atoms or a substituted alkyl group having 1 to 30 carbon atoms, Metal coordination compounds.
<9> R ³ to R ⁴⁷ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, a cyano group, an amino group, a heterocyclic group, an acyl group, a hydroxyl group, or a trifluoromethyl group. The metal coordination compound according to any one of 1 to 8, which is selected from the group consisting of:
<10> R ⁵ and R ¹⁰ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, a cyano group, an amino group, a heterocyclic group, an acyl group, a hydroxyl group, or a trifluoromethyl group 10. The metal coordination compound according to any one of 1 to 9, which is selected from the group consisting of:
<11> The metal coordination compound according to any one of 1 to 10, wherein M is iridium.
<12> A light emitting material comprising the metal coordination compound according to any one of 1 to 11 above.
<13> A light emitting device using the light emitting material as described in 12 above.
<14> The intermediate of the metal coordination compound according to any one of 1 to 11 represented by the general formula (9).

(In the general formula (9), M represents iridium or platinum. N represents a nitrogen atom. When M is iridium, m ¹ = 2 and when M is platinum, m ¹ = 1. R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a substituent, and adjacent substituents may combine to form a ring structure, and X represents a halogen atom.)

  Since the novel metal coordination compound of the present invention efficiently emits light in the visible light region (particularly the red region) with low power consumption, a light-emitting device using the compound is a display device, a display, a back light Suitable for fields such as light, electrophotography, illumination light source, recording light source, exposure light source, reading light source, sign, signboard, interior. The compounds of the present invention can also be applied to medical uses, photographic materials, UV absorbing materials, laser dyes, color filter dyes, color conversion filters, optical communications, and the like.

  The metal coordination compound according to the present invention is represented by the above general formula (1) or (2), and these metal coordination compounds are contained in a light emitting layer of a light emitting element or a plurality of organic compound layers including a light emitting layer. Thus, a light emitting element having a light emission color excellent in the visible light region (particularly the red region) can be obtained. A high-efficiency white light-emitting element can also be produced by combining a blue to green light-emitting element on the basis of a red light-emitting element using the compound of the present invention.

  Hereinafter, the present invention will be described in more detail.

（一般式（１０）中、Ｎは窒素原子を表す。Ｒ^１〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。） The metal coordination compound of the present invention is characterized by having a bidentate ligand represented by the following general formula (10).

(In General Formula (10), N represents a nitrogen atom. R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a substituent. Adjacent substituents are bonded to form a ring structure. May be.)

That is, when the bidentate ligand represented by the general formula (10) and the central metal iridium or platinum form a bond, a term from the excited singlet state to the excited triplet state is caused by the heavy atom effect. As a result, the metal coordination compound of the present invention efficiently emits phosphorescence in the visible light region (particularly the red region) in a solution state or a solid state.
As a feature of the compound of the present invention, the above-described tris (2-phenylpyridine) iridium complex exhibits relatively weak luminescence even when irradiated with ultraviolet light in the solid state, whereas the compound of the present invention is strong in the solid state. It was revealed that phosphorescence was exhibited (see Examples 48 to 52). Therefore, this invention compound can be used suitably as a luminescent material of solid light emitting devices, such as an organic electroluminescent element.

  The metal coordination compound of the present invention may be represented by either the general formula (1) or (2), and is described in isomers (for example, facial isomers, meridional isomers, and JP-A-2006-278781). Isomers, etc.).

  The metal coordination compound of the present invention is a neutral metal coordination compound or an ionic metal coordination compound, more preferably a neutral metal coordination compound.

  Among the metal coordination compounds of the present invention, those having an emission quantum yield in solution of 0.01 or more are preferred, those of 0.1 or more are more preferred, and those of 0.2 or more are particularly preferred.

  In order to remove dissolved oxygen, the measurement of the luminescence quantum yield in the solution is carried out after passing an inert gas (argon gas, nitrogen gas) through the solution in which the luminescent material is dissolved, or the solution in which the luminescent material is dissolved. This should be done after freezing and degassing. As a method for measuring the luminescence quantum yield, either an absolute method or a relative method may be used. In the relative method, the luminescence quantum yield can be measured by comparing the emission spectrum with a standard substance (such as quinine sulfate). In the absolute method, it is possible to measure the luminescence quantum yield in solution or in a solid state by using a commercially available device (Absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd.). Although the luminescence quantum yield in a solution can be measured using various solvents, the metal coordination compound according to the present invention only needs to achieve the luminescence quantum yield in any solvent.

  Among the metal coordination compounds of the present invention, the emission maximum wavelength of the emission spectrum is preferably in the range of 400 nm to 900 nm, more preferably in the range of 550 nm to 750 nm, particularly preferably in the range of 600 nm to 700 nm, The thing of the range of 600 nm-650 nm is the most preferable.

  The metal coordination compound of the present invention is preferably red luminescent.

The symbols (M, m, m ¹ , n, Q, k, X, L, and R ^{1 to} R ⁴⁷ ) described in the general formulas (1) to (10) will be described below.

  M represents iridium or platinum, and iridium is preferred.

  The valence of M is preferably trivalent when M is iridium. Divalent is preferable when M is platinum.

m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n = 2 or 3. When M is iridium, m + n = 3, m = 2 or 3 is preferable, and n = 0 or 1 is preferable. When M is platinum, m + n = 2, m = 1 or 2 is preferable, and n = 0 or 1 is preferable.
For m ¹ , m ¹ = 2 when M is iridium, and m ¹ = 1 when M is platinum.

Q represents a counter anion. The counter anion is not particularly limited, but preferably an alkali metal ion, alkaline earth metal ion, halogen ion, perchlorate ion, PF ₆ ion, ammonium ion, CF ₃ CF ₂ CF ₂ COO ion, SbF ₆ ion, Dicyanamide ion, bis (trifluoromethanesulfonyl) amide ion, borate ion or phosphonium ion.

k represents an integer of 0-2. k is preferably 0 or 1, more preferably 0.
X represents a halogen atom, specifically, a chlorine atom, a bromine atom or an iodine atom is preferred, a chlorine atom or a bromine atom is more preferred, and a chlorine atom is particularly preferred.

  L represents a bidentate ligand. Neutral bidentate ligands or anionic bidentate ligands are preferred, anionic bidentate ligands are more preferred, and monoanionic bidentate ligands are particularly preferred.

  L represents a bidentate ligand that forms an M-nitrogen bond and an M-carbon bond, a bidentate ligand that forms an M-nitrogen bond and an M-oxygen bond, and two M-oxygen bonds. Bidentate ligand, preferably bidentate ligand that forms two M-nitrogen bonds, bidentate ligand that forms M-nitrogen bond and M-carbon bond, M-nitrogen bond and M- More preferably a bidentate ligand that forms an oxygen bond, a bidentate ligand that forms two M-oxygen bonds, a bidentate ligand that forms an M-nitrogen bond and an M-oxygen bond, A bidentate ligand that forms two M-oxygen bonds is particularly preferable.

Examples of the bidentate ligand that forms an M-nitrogen bond and an M-carbon bond include 2-phenylpyridine derivatives, 2-phenylquinoline derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives, 2- (2 -Benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative, 1-phenyl-1H-indazole derivative, 2-phenylbenzothiazole derivative, 2-phenylthiazole derivative, 2-phenylbenzoxazole derivative, 2 -Phenyloxazole derivatives, 2-furanylpyridine derivatives, 2- (2-benzofuranyl) pyridine derivatives, 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f , h] quinoxaline derivatives, benzo [h] − 5,6-dihydroquinoline derivatives, 9- (2-pyridyl) carbazole derivatives, 1- (2-pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivative, 2- (1-naphthyl) quinoline derivative, 3- (1-naphthyl) isoquinoline derivative, 3- (2-naphthyl) isoquinoline derivative, 2- (1-naphthyl) pyridine derivative, 2- (2-naphthyl) pyridine derivatives, 6-phenylphenanthridine derivatives, 6- (1-naphthyl) phenanthridine derivatives, 6- (2-naphthyl) phenanthridine derivatives, benzo [c] acridine derivatives, benzo [c ] Phenazine derivatives, dibenzo [a, c] acridine derivatives, dibenzo [a, c] phenazine derivatives, 2-phenylquinoki Sarin derivative, 2,3-diphenylquinoxaline derivative, 2-benzylpyridine derivative, 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltriazole derivative, 5- It is a phenyltetrazole derivative or a 2-alkenylpyridine derivative.
Preferably, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 1- (1-naphthyl) isoquinoline derivative, 1- (2-naphthyl) isoquinoline derivative, 2- (2-naphthyl) quinoline derivative, 2- (1-naphthyl) quinoline derivative, 3- (1-naphthyl) isoquinoline derivative, 3- (2-naphthyl) isoquinoline derivative, 2- (1-naphthyl) pyridine derivative 2- (2-naphthyl) pyridine derivative, 6-phenylphenanthridine derivative, 6- (1-naphthyl) phenanthridine derivative, 6- (2-naphthyl) phenanthridine derivative, benzo [c] acridine derivative, Benzo [c] phenazine derivative, dibenzo [a, c] acridine derivative, dibenzo [a, c] phenazine derivative, 2-phenylquinoxaline derivative, 2,3-diphenylquinoxaline derivative, 2-benzylpyridine derivative, 2-phenylbenzimidazole Derivatives or 1-phenylimidazole derivatives.
More preferably, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole Derivatives, 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1 -Naphthyl) quinoline derivative, 3- (1-naphthyl) isoquinoline derivative, 3- (2-naphthyl) isoquinoline derivative, 2- (1-naphthyl) pyridine derivative, 2- (2-naphthyl) pyridine derivative, benzo [c] Acridine derivatives, benzo [c] phenazine derivatives, dibenzo [a, c] acridine derivatives Dibenzo [a, c] phenazine derivatives, 2-phenyl-quinoxaline derivatives, 2,3-diphenyl quinoxaline derivatives, 2-phenyl-benzimidazole derivatives, or a 1-phenylimidazole derivative.
Particularly preferably, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 7,8-benzoquinoline derivative, 7,8-benzoquinoxaline derivative, dibenzo [f, h] Quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) quinoline derivatives, benzo [c] acridine derivatives, benzo [c] phenazine derivatives, 2-phenylquinoxaline Derivatives, 2,3-diphenylquinoxaline derivatives, 2-phenylbenzimidazole derivatives, or 1-phenylimidazole derivatives.
Most preferred is a 2-phenylpyridine derivative, a 2-phenylquinoline derivative, or a 1-phenylisoquinoline derivative.

  Specifically, International Publication WO 2004-085450, International Publication WO 2006-075905, International Publication WO 2002-44189, International Publication WO 2002-45466, International Publication WO 2006-046980, International Publication WO 2006-059758, Patent Publication 2006. -182727, patent publication 2006-151888, patent publication 2006-151877, patent publication 2006-93665, patent publication 2006-1000039, international publication WO2004-101707, international publication WO2005-073339, international publication WO2005. 056719, International Publication WO2005-056716, International Publication WO2005-056715, International Publication WO2005-048315, International Publication WO2005-033244 International Publication WO 2004-081019, International Publication WO 2004-045000, International Publication WO 2004-044089, International Publication WO 2004-026886, Patent Publication 2002-234894, Patent Publication 2002-226495, Patent Publication 2003-59667, Patent Publication 2001-345183, Patent Publication 2001-247859, Patent Publication 2003-7469, Patent Publication 2003-73388, Patent Publication 2003-109758, Patent Publication 2003-123982, Patent Publication 2003-133074, Patent Publication No. 2003-131464, Patent Publication No. 2003-131463, Patent Publication No. 2004-107441, Patent Publication No. 2004-67658, Patent Publication No. 2003-342284, Patent Publication No. 2 No. 05-29784, Japanese Patent Publication No. 2005-29783, Japanese Patent Publication No. 2005-29782, Japanese Patent Publication No. 2005-23072, Japanese Patent Publication No. 2005-23071, Japanese Patent Publication No. 2005-23070, Japanese Patent Publication No. 2005-2101, Japanese Patent Publication No. 2005. -2053, Patent Publication No. 2005-78996, Patent Publication No. 2005-68110, Patent Publication No. 2005-60374, Patent Publication No. 2005-44802, Patent Publication No. 2005-29785, Patent Publication No. 2005-104843, Patent Publication No. 2005- No. 97549, Japanese Patent Publication No. 2005-220136, Japanese Patent Publication No. 2005-213348, Japanese Patent Publication No. 2005-170851, Japanese Patent Publication No. 2005-163036, Japanese Patent Publication No. 2005-154396, Japanese Patent Publication No. 2005-272411. No., Japanese Patent Publication No. 2005-327526, Japanese Patent Publication No. 2005-325048, Japanese Patent Publication No. 2005-314663, Japanese Patent Publication No. 2006-13222, Japanese Patent Publication No. 2006-8688, Japanese Patent Publication No. 2006-80419, Japanese Patent Publication No. 2006-76969. International Publication WO2002-15645, International Publication WO2002-02714, International Publication WO2002-0664700, International Publication WO2003-033617, International Publication WO2003-000661, International Publication WO2002-081488, US Patent Publication 2006-0251923. There is a description.

  Examples of structural formulas of bidentate ligands that form an M-nitrogen bond and an M-carbon bond are shown in Tables 1 and 2, but the present invention is not limited thereto. R in Tables 1 and 2 is a hydrogen atom or a substituent.

The bidentate ligand that forms an M-nitrogen bond and an M-oxygen bond is, for example, a picolinic acid derivative, a pyridinesulfonic acid derivative, a quinolinesulfonic acid derivative, or a quinolinecarboxylic acid derivative. A picolinic acid derivative or a pyridinesulfonic acid derivative is preferable.
Specifically, Patent Publication No. 2006-16394, Patent Publication No. 2006-307210, Patent Publication No. 2006-298900, International Publication No. WO2006-028224, International Publication No. WO2006-097717, Patent Publication No. 2004-111379, Patent Publication No. 2005 -29785 and the like.

Examples of the bidentate ligand that forms two M-oxygen bonds are β-diketone derivatives, carboxylic acid derivatives, and tropolone derivatives. Preferred are β-diketone derivatives or carboxylic acid derivatives, more preferred are β-diketone derivatives, and particularly preferred are pentane-2,4-dione and 1,3-diphenylpropane-1,3-. Dione, 2,2,6,6-tetramethylheptane-3,5-dione, most preferably pentane-2,4-dione.
Specific examples include Patent Publication No. 2005-35902, Patent Publication No. 2004-349224, Patent Publication No. 2006-28101, and Patent Publication No. 2005-29785.

Examples of bidentate ligands that form two M-nitrogen bonds include 2,2′-bipyridine derivatives, 1,10-phenanthroline derivatives, 2,2′-biquinoline derivatives, and 2,2′-dipyridylamine derivatives. Imidazole derivatives, pyrazolylborate derivatives, pyrazole derivatives. Preferred are 2,2′-bipyridine derivatives, 1,10-phenanthroline derivatives, or 2,2′-dipyridylamine derivatives.
Specific examples include Patent Publication No. 2005-29883, Patent Publication No. 2006-213720, and Japanese Patent Application Laid-Open No. 2003-133074.

R ^{1 to} R ⁴⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl. , N-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon atoms). 2 to 10 such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably carbon number) To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and the like, and amino groups (preferably having 0 to 0 carbon atoms). 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, and the like. (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like), aryloxy Group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably carbon 6-12, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1-30 carbons, more preferably having 1-20 carbons, especially Preferably it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc.), an acyl group (preferably C1-C30, more preferably C1-C20, especially preferably carbon) 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 2 carbon atoms). 12 and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like. Xoxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxyl group, Mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, trifluoromethyl group, hydroxamic acid group, sulfino group, hydrazino group, Imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, For example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like can be mentioned. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl, triphenylsilyl, etc.), a silyloxy group (preferably C3-C40, More preferably C3-C30, Most preferably C3-C24, for example, trimethylsilyloxy, triphenylsilyloxy, etc.) are mentioned.
Among these, particularly preferred substituents are a cyano group, a trifluoromethyl group, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. Group, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted acyl group having 1 to 12 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, substituted or unsubstituted An amino group having 0 to 10 carbon atoms, or a substituted or unsubstituted heterocyclic group having 1 to 12 carbon atoms. Note that a hydrogen atom in the substituent may be replaced with a fluorine atom.

Further, two or more adjacent R ^{1 to} R ⁴⁷ are preferably connected to each other to form a saturated or unsaturated carbocyclic ring or a saturated or unsaturated heterocyclic ring.

（一般式（１１）中、Ｎは窒素原子を表す。Ｒ^３〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。環Ａは飽和炭素環を表す。飽和炭素環には置換基がついても良い） R ¹ and R ² are preferably combined to form a saturated carbocyclic ring (ring A in the general formula (11)). That is, among the bidentate ligands represented by the general formula (10), the bidentate ligand represented by the general formula (11) is preferably used. The saturated carbocycle (ring A) may be substituted.

(In General Formula (11), N represents a nitrogen atom. R ^{3 to} R ¹¹ each independently represent a hydrogen atom or a substituent. Adjacent substituents are bonded to form a ring structure. Ring A represents a saturated carbocycle, which may be substituted.

  The ring A is preferably a saturated carbocycle having 3 to 20 carbon atoms, more preferably a saturated carbocycle having 3 to 15 carbon atoms, and a saturated carbocycle having 3 to 10 carbon atoms. Particularly preferred is a saturated carbocyclic ring having 5 to 8 carbon atoms.

R ¹ and R ² are preferably each independently an alkyl group having 1 to 30 carbon atoms or a substituted alkyl group having 1 to 30 carbon atoms, and an alkyl group or carbon having 1 to 20 carbon atoms. A substituted alkyl group having 1 to 20 atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group having 1 to 10 carbon atoms is particularly preferable.

When R ¹ and R ² are combined to form a saturated carbocycle, or when R ¹ and R ² are each independently an alkyl group or a substituted alkyl group, the metal coordination compound of the present invention The solubility in a solvent is greatly improved. The improvement in solubility in a solvent is very advantageous when a light-emitting element is produced using a coating process, and can be suitably used.

R ²⁸ and R ²⁹ are particularly preferably an alkyl group or an aryl group, and most preferably an alkyl group.

It is also preferred that R ³³ and R ³⁴ combine to form a condensed ring. As for the ligand represented by the general formula (7), R ³³ and R ³⁴ are particularly preferably bonded to form a 1,10-phenanthroline skeleton.

R ⁴² is particularly preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and most preferably an alkyl group or an aryl group.

R ⁴⁷ is particularly preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

  Compared with the tris (2-phenylpyridine) iridium complex, the compound of the present invention has a longer wavelength shift in light emission and exhibits particularly excellent emission characteristics in the red region. As a feature of the bidentate ligand represented by the general formula (10), it has two nitrogen atoms on the five-membered ring, and further, two phenyl groups are bonded to the five-membered ring, and the ring conjugated system Is expanded. The inventor speculates that such a unique molecular structure of the bidentate ligand has an effect on the longer wavelength of light emission.

  Moreover, about the metal coordination compound of this invention, it is possible to adjust the light emission wavelength by changing the above-mentioned ligand L. FIG. In this technical field, it is considered that the ligand L does not directly contribute to the light emission characteristics of the metal coordination compound, but can slightly change the light emission characteristics, and is called an auxiliary ligand (for example, patents). (See publication 2006-513278).

  On the other hand, it is considered that the bidentate ligand represented by the general formula (10) mainly contributes to the development of the light emission characteristics (red light emission characteristics) of the metal coordination compound of the present invention as described above. . Therefore, by combining the bidentate ligand represented by the general formula (10) and a conventionally known auxiliary ligand, the emission wavelength can be changed according to the use centering on the red region.

Furthermore, it becomes possible to control the emission wavelength of the metal coordination compound of the present invention by introducing a substituent into R ^{3 to} R ^{11 of the} bidentate ligand represented by the general formula (10). For example, as described in the examples, when an electron-withdrawing fluorine atom is introduced into R ⁵ and R ¹⁰ , light emission is shifted by a short wavelength (see Table 3).

  In addition, an alkyl group (for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl) is added to the bidentate ligand represented by the general formula (10). , Cyclohexyl, etc.) can improve the solubility of the metal coordination compound of the present invention in a solvent. The improvement in solubility in a solvent is advantageous when a light-emitting element is produced using a coating process, and can be suitably used. Moreover, by introducing a trifluoromethyl group or fluorine substituent into a bidentate ligand having a cyclopenta [de] quinoline skeleton, it is possible to reduce the intermolecular interaction and improve the sublimation property of the compound of the present invention. It is. In this case, it is advantageous in a film forming process by vacuum vapor deposition for producing a light emitting element.

  In addition, the metal coordination compound represented by the general formula (1) or (2) may be a low molecular compound, or a partial structure represented by the general formula (1) or (2). You may use as a so-called oligomer compound and polymer compound (The mass mean molecular weight (polystyrene conversion) becomes like this. Preferably it is 1000-5 million, More preferably, it is 2000-1 million, More preferably, it is 3000-100000.). . Examples of the polymerization method include methods described in JP-A Nos. 2003-119179, 2003-171391, 2003-113246, 2003-206320, and 2003-147021.

  Further, the metal coordination compound represented by the general formula (1) or (2) can also be used as a so-called dendrimer having a structure regularly branched from the center. Examples of the light-emitting dendrimer containing a metal complex are described in JP-T-2004-530254, JP-T-2005-521210, JP-T-2005-537321, JP-A-2006-188673, and WO2005 / 026144.

  That is, a luminescent polymer and a luminescent dendrimer can be produced by using the metal coordination compound represented by the general formula (1) or (2) as a luminescent material by the above-described method.

Desirable examples of the bidentate ligand represented by the general formula (10) or (11) are shown in Tables 4 to 9.

The bidentate ligand represented by the general formula (10) or (11) is synthesized as in the formula (A) with reference to the method described in Tetrahedron Asymmetry, 1995, Vol. 6, page 3. be able to.

（一般式（Ｂ）〜（Ｄ）中、Ｎは窒素原子を表す。Ｒ^１〜Ｒ^１１は、各々独立に、水素原子または置換基を表す。また、隣接する置換基は結合して環構造を形成してもよい。Ｌは２座配位子を表す。） In order to produce the compound of the present invention represented by the general formula (1) or (2), for example, according to the formula (B) to the formula (D), a conventional method (in the presence or absence of a solvent, in the presence of a base) In the presence or absence, the reaction may be performed at room temperature or with heating in the presence or absence of a silver compound as a dehalogenating agent. Specifically, reacting a metal raw material such as iridium trichloride, iridium hexachloride, potassium tetrachloroplatinate, and first platinum chloride with a bidentate ligand represented by the general formula (10) in a solvent. First, a method of synthesizing a crosslinked dimer represented by the general formula (9) and reacting this with an organic ligand represented by the general formula (10) (formula (B)) or the general formula (9) There is a method (formulas (C) and (D)) for reacting the cross-linked dimer represented by the formula (I) with the ligand L. The above reaction is preferably performed in a nitrogen atmosphere or an argon atmosphere. Further, the heating means is not particularly limited, but it is also preferable to irradiate microwaves in order to facilitate the reaction. Although there is no restriction | limiting in particular in the wavelength of a microwave, It is 2000-3000 MHz, Preferably it is 2400-2500 MHz. As the microwave oscillation apparatus, all commercially available reaction apparatuses for organic synthesis can be applied. Moreover, you may use an oil bath, a mantle heater, etc. as a heating means.

(In general formulas (B) to (D), N represents a nitrogen atom. R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a substituent. Adjacent substituents are bonded to form a ring structure. L represents a bidentate ligand.)

  In addition, it is desirable to use a reaction solvent in order to further facilitate the reaction for synthesizing the metal coordination compound according to the present invention. Although there is no restriction | limiting in particular as such a solvent, An alcohol solvent, a protic solvent, an aprotic solvent, a nitrile solvent etc. are used preferably. Although the reaction temperature, reaction pressure, and reaction time vary depending on the raw materials and solvents used, the reaction temperature is usually 40 to 250 ° C., preferably 50 to 230 ° C., more preferably 60 to 220 ° C., and the reaction pressure is 1 to 30 atm, preferably 1 to 5 atm.

  The metal coordination compound according to the present invention can be provided after treatment according to the post-treatment of a normal synthesis reaction, and if necessary, purified or not purified. As a post-treatment method, for example, extraction, cooling, crystallization by adding water or an organic solvent, an operation of distilling off the solvent from the reaction mixture, and the like can be performed alone or in combination. As a purification method, recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.

Below, although the representative example of the metal coordination compound shown by the said General formula (1) or (2) based on this invention is shown, this invention is not limited to these.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to this. A method for synthesizing the compound of the present invention is shown below.

引き続き、このダイマーを１０５ｍｇ、ピコリン酸ナトリウムを３４ｍｇ、２−エトキシエタノール１５ｍｌと水１ｍｌをナスフラスコに入れ、アルゴン雰囲気下でマイクロ波（２４５０ＭＨｚ）を１５分間照射した。反応溶液を室温まで冷却した後、溶媒を減圧濃縮し赤茶色固体を得た。この赤茶色固体をジクロロメタン−ヘキサンで再結晶し、所望のイリジウム錯体（Ａ−２４）を得た。単離収率は７０％であった。

¹H-NMR (CDCl₃中)δ8.33 (d, 1H), 7.98 (t, 1H), 7.89 (d, 1H), 7.73 (d, 2H), 7.69 (d, 2H), 7.52-7.60 (m, 6H), 7.41 (t, 1H), 7.33 (d, 1H), 7.21 (d, 1H), 6.71-6.80 (m, 4H), 6.63 (t, 1H), 6.50 (d, 1H), 2.85 (dd, 1H), 1.26-1.99 (m, 17H), 0.25-0.34 (m, 1H), 0.20 (d, 1H). Example 1 (Synthesis of the present compound (A-24))
502 mg of iridium trichloride trihydrate, 1 g of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene (manufactured by Aldrich, Table 4 (L-2)), 2- 40 ml of ethoxyethanol and 10 ml of water were placed in a two-necked flask and heated to reflux for 22 hours under an argon atmosphere. The reaction solution was cooled to room temperature, then concentrated under reduced pressure, and water was added to obtain a reddish brown solid that was produced by filtration. The reddish brown solid was separated and purified by silica gel chromatography (eluent: dichloromethane, ethyl acetate) to obtain an intermediate dimer. The isolation yield was 29%.

Subsequently, 105 mg of this dimer, 34 mg of sodium picolinate, 15 ml of 2-ethoxyethanol and 1 ml of water were placed in an eggplant flask and irradiated with microwaves (2450 MHz) for 15 minutes in an argon atmosphere. After the reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure to obtain a reddish brown solid. This reddish brown solid was recrystallized from dichloromethane-hexane to obtain a desired iridium complex (A-24). The isolation yield was 70%.

¹ H-NMR (in CDCl ₃ ) δ 8.33 (d, 1H), 7.98 (t, 1H), 7.89 (d, 1H), 7.73 (d, 2H), 7.69 (d, 2H), 7.52-7.60 ( m, 6H), 7.41 (t, 1H), 7.33 (d, 1H), 7.21 (d, 1H), 6.71-6.80 (m, 4H), 6.63 (t, 1H), 6.50 (d, 1H), 2.85 (dd, 1H), 1.26-1.99 (m, 17H), 0.25-0.34 (m, 1H), 0.20 (d, 1H).

¹H-NMR (CDCl₃中)δ7.74 (d, 4H), 7.52-7.57 (m, 6H), 7.18 (d, 2H), 6.65 (t, 2H), 6.56 (t, 2H), 6.52 (d, 2H), 5.70 (s, 1H), 2.60-2.70 (m, 4H), 1.81-2.07 (m, 18H), 1.21-1.30 (m, 2H), 1.10 (d, 2H). Example 2 (Synthesis of Compound (A-47) of the present invention)
201 mg of the dimer synthesized in Example 1, 46 mg of sodium acetylacetone, 20 ml of 2-ethoxyethanol and 1 ml of water were placed in an eggplant flask and irradiated with microwaves (2450 MHz) for 15 minutes in an argon atmosphere. After the reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure to obtain a reddish brown solid. This reddish brown solid was recrystallized from methanol-water to obtain a desired iridium complex (A-47).

¹ H-NMR (in CDCl ₃ ) δ 7.74 (d, 4H), 7.52-7.57 (m, 6H), 7.18 (d, 2H), 6.65 (t, 2H), 6.56 (t, 2H), 6.52 ( d, 2H), 5.70 (s, 1H), 2.60-2.70 (m, 4H), 1.81-2.07 (m, 18H), 1.21-1.30 (m, 2H), 1.10 (d, 2H).

¹H-NMR (CDCl₃中)δ8.89 (d, 2H), 8.31 (t, 2H), 8.03 (d, 2H), 7.68 (d, 4H), 7.53-7.61 (m, 8H), 7.42 (d, 2H), 6.96 (t, 2H), 6.86 (t, 2H), 6.76 (d, 2H), 1.84 (brs, 4H), 1.61 (brs, 4H), 1.40-1.43 (m, 2H), 1.25-1.30 (m, 2H), 0.82-0.90 (m, 4H), 0.31-0.37 (m, 2H), 0.15 (d, 2H).
ESI-MS (m/z): 924 Example 3 (Synthesis of Compound (A-93) of the present invention)
104 mg of the dimer synthesized in Example 1, 26 mg of 2,2′-bipyridine, and 15 ml of 2-ethoxyethanol were placed in an eggplant flask, and irradiated with microwaves (2450 MHz) for 5 minutes in an argon atmosphere. After cooling the reaction solution to room temperature, the solvent was concentrated under reduced pressure, a saturated aqueous NH ₄ PF ₆ solution was added, and the resulting reddish brown solid was recrystallized from dichloromethane-hexane. Identified using proton NMR and electrospray ionization mass spectrometry (ESI-MS). The isolation yield was 67%.

¹ H-NMR (in CDCl ₃ ) δ 8.89 (d, 2H), 8.31 (t, 2H), 8.03 (d, 2H), 7.68 (d, 4H), 7.53-7.61 (m, 8H), 7.42 ( d, 2H), 6.96 (t, 2H), 6.86 (t, 2H), 6.76 (d, 2H), 1.84 (brs, 4H), 1.61 (brs, 4H), 1.40-1.43 (m, 2H), 1.25 -1.30 (m, 2H), 0.82-0.90 (m, 4H), 0.31-0.37 (m, 2H), 0.15 (d, 2H).
ESI-MS (m / z): 924

ESI-MS (m/z): 939 Example 4 (Synthesis of Compound (A-110) of the Present Invention)
101 mg of the dimer synthesized in Example 1, 27 mg of 2,2′-dipyridylamine, and 15 ml of 2-ethoxyethanol were placed in an eggplant flask and irradiated with microwaves (2450 MHz) for 15 minutes in an argon atmosphere. After cooling the reaction solution to room temperature, the solvent was concentrated under reduced pressure, a saturated aqueous NH ₄ PF ₆ solution was added, and the resulting reddish brown solid was recrystallized from dichloromethane-hexane. Identified using proton NMR and electrospray ionization mass spectrometry (ESI-MS). The isolation yield was 82%.

ESI-MS (m / z): 939

¹H-NMR (CDCl₃中)δ7.49 (q, 4H), 7.06 (t, 4H), 1.92-1.97 (m, 4H), 1.79 (brs, 4H), 1.73 (brs, 2H).
引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−９）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は５１％であった。

引き続き、実施例１で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例１と同様の方法を用いて、所望のイリジウム錯体（Ａ−２５）を得た。単離収率は８９％であった。

¹H-NMR (CDCl₃中)δ8.34 (d, 1H), 8.02 (t, 1H), 7.89 (d, 1H), 7.67-7.73 (m, 4H), 7.46 (t, 1H), 7.34 (t, 1H), 7.21-7.28 (m, 5H), 6.52 (t, 1H), 6.39-6.45 (m, 2H), 6.11 (d, 1H), 2.80 (dd, 1H), 1.62-1.97 (m, 14H), 1.42-1.49 (m, 1H), 1.37 (d, 1H), 1.22 (dd, 1H), 0.25-0.34 (m, 1H), 0.18 (d, 1H). Example 5 (Synthesis of the present compound (A-25))
2 g of 4,4′-difluorobenzyl, 803 mg of cyclohexanone, 8 g of ammonium acetate, and 20 ml of acetic acid were reacted by heating at 120 ° C. for 1 hour. After cooling to room temperature, water (about 200 ml) was added until a precipitate formed in the reaction solution. This precipitate was washed with water and recrystallized with methanol-water to obtain the desired ligand (L-9). The isolation yield was 69%.

¹ H-NMR (in CDCl ₃ ) δ 7.49 (q, 4H), 7.06 (t, 4H), 1.92-1.97 (m, 4H), 1.79 (brs, 4H), 1.73 (brs, 2H).
Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-9) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 51%.

Subsequently, a desired iridium complex (A-25) was obtained using the same method as in Example 1 except that the above dimer was used instead of the dimer used in Example 1. The isolation yield was 89%.

¹ H-NMR (in CDCl ₃ ) δ 8.34 (d, 1H), 8.02 (t, 1H), 7.89 (d, 1H), 7.67-7.73 (m, 4H), 7.46 (t, 1H), 7.34 ( t, 1H), 7.21-7.28 (m, 5H), 6.52 (t, 1H), 6.39-6.45 (m, 2H), 6.11 (d, 1H), 2.80 (dd, 1H), 1.62-1.97 (m, 14H), 1.42-1.49 (m, 1H), 1.37 (d, 1H), 1.22 (dd, 1H), 0.25-0.34 (m, 1H), 0.18 (d, 1H).

¹H-NMR (CDCl₃中)δ7.73 (dd, 4H), 7.25 (t, 4H), 7.18 (dd, 2H), 6.35 (dd, 2H), 6.13 (d, 2H), 5.72 (s, 1H), 2.53-2.64 (m, 4H), 1.81-2.11 (m, 18H), 1.19-1.29 (m, 2H), 1.08 (d, 2H). Example 6 (Synthesis of Compound (A-48) of the Present Invention)
A desired iridium complex (A-48) was obtained in the same manner as in Example 2, except that the dimer synthesized in Example 5 was used instead of the dimer used in Example 2. The isolation yield was 56%.

¹ H-NMR (in CDCl ₃ ) δ 7.73 (dd, 4H), 7.25 (t, 4H), 7.18 (dd, 2H), 6.35 (dd, 2H), 6.13 (d, 2H), 5.72 (s, 1H), 2.53-2.64 (m, 4H), 1.81-2.11 (m, 18H), 1.19-1.29 (m, 2H), 1.08 (d, 2H).

ESI-MS (m/z):996 Example 7 (Synthesis of the present compound (A-94))
A desired iridium complex (A-94) was obtained in the same manner as in Example 3 except that the dimer synthesized in Example 5 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 996

¹H-NMR (CDCl₃中)δ7.40 (d, 4H), 7.15 (d, 4H), 2.38 (s, 6H), 1.92-1.97 (m, 4H), 1.88 (brs, 4H), 1.70-1.74 (brs, 2H).
引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−１０）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は３８％であった。

引き続き、実施例１で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例１と同様の方法を用いて、所望のイリジウム錯体（Ａ−２９）を得た。単離収率は３１％であった。

¹H-NMR (CDCl₃中)δ8.30 (d, 1H), 7.95 (t, 1H), 7.87 (d, 1H), 7.56-7.60 (m, 4H), 7.39 (t, 1H), 7.31-7.34 (m, 4H), 7.24 (d, 1H), 7.15 (d, 1H), 6.61 (s, 1H), 6.55 (d, 1H), 6.46 (d, 1H), 6.34 (s, 1H), 2.79-2.84 (m, 1H), 2.47 (s, 3H), 2.46 (s, 3H), 2.19 (s, 3H), 2.10 (s, 3H), 1.55-1.97 (m, 14H), 1.44 (d, 1H), 1.35 (d, 1H), 1.23-1.30 (m, 1H), 0.27-0.32 (m, 1H), 0.16 (d, 1H). Example 8 (Synthesis of Compound (A-29) of the present invention)
The desired ligand (L-10) was obtained in the same manner as in Example 5 except that 4,4′-dimethylbenzyl was used instead of 4,4′-difluorobenzyl. The isolation yield was 51%.

¹ H-NMR (in CDCl ₃ ) δ 7.40 (d, 4H), 7.15 (d, 4H), 2.38 (s, 6H), 1.92-1.97 (m, 4H), 1.88 (brs, 4H), 1.70- 1.74 (brs, 2H).
Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-10) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 38%.

Subsequently, a desired iridium complex (A-29) was obtained in the same manner as in Example 1 except that the above dimer was used instead of the dimer used in Example 1. The isolation yield was 31%.

¹ H-NMR (in CDCl ₃ ) δ 8.30 (d, 1H), 7.95 (t, 1H), 7.87 (d, 1H), 7.56-7.60 (m, 4H), 7.39 (t, 1H), 7.31- 7.34 (m, 4H), 7.24 (d, 1H), 7.15 (d, 1H), 6.61 (s, 1H), 6.55 (d, 1H), 6.46 (d, 1H), 6.34 (s, 1H), 2.79 -2.84 (m, 1H), 2.47 (s, 3H), 2.46 (s, 3H), 2.19 (s, 3H), 2.10 (s, 3H), 1.55-1.97 (m, 14H), 1.44 (d, 1H ), 1.35 (d, 1H), 1.23-1.30 (m, 1H), 0.27-0.32 (m, 1H), 0.16 (d, 1H).

¹H-NMR (CDCl₃中)δ7.62 (d, 4H), 7.33 (d, 4H), 7.11 (d, 2H), 6.39 (d, 2H), 6.35 (s, 2H), 5.66 (s, 1H), 2.58-2.67 (m, 4H), 2.46 (s, 6H), 1.83-2.10 (m, 24H), 1.21-1.29 (m, 2H), 1.06 (d, 2H). Example 9 (Synthesis of the present compound (A-52))
A desired iridium complex (A-52) was obtained in the same manner as in Example 2 except that the dimer synthesized in Example 8 was used instead of the dimer used in Example 2. The isolation yield was 35%.

¹ H-NMR (in CDCl ₃ ) δ7.62 (d, 4H), 7.33 (d, 4H), 7.11 (d, 2H), 6.39 (d, 2H), 6.35 (s, 2H), 5.66 (s, 1H), 2.58-2.67 (m, 4H), 2.46 (s, 6H), 1.83-2.10 (m, 24H), 1.21-1.29 (m, 2H), 1.06 (d, 2H).

ESI-MS (m/z):980 Example 10 (Synthesis of Compound (A-97) of the present invention)
A desired iridium complex (A-97) was obtained in the same manner as in Example 3 except that the dimer synthesized in Example 8 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 980

¹H-NMR (CDCl₃中)δ7.51 (d, 4H), 7.43 (t, 2H), 7.36 (t, 4H), 2.14-2.21 (m, 8H).
引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−１）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は４１％であった。

実施例２で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例２と同様の方法を用いて、所望のイリジウム錯体（Ａ−５０）を得た。単離収率は３９％であった。

¹H-NMR (CDCl₃中)δ7.76 (d, 4H), 7.51-7.57 (m, 6H), 7.22 (d, 2H), 6.69 (t, 2H), 6.58 (t, 2H), 6.44 (d, 2H), 5.62 (s, 1H), 2.99-3.06 (m, 2H), 2.70-2.76 (m, 2H), 2.14-2.33 (m, 6H), 1.92-2.08 (m, 4H), 1.85 (s, 6H), 1.63-1.68 (m, 2H). Example 11 (Synthesis of Compound (A-50) of the present invention)
The desired ligand (L-1) was obtained by the same method as in Example 5 except that benzyl was used instead of 4,4′-difluorobenzyl and cyclopentanone was used instead of cyclohexanone. It was. The isolation yield was 33%.

¹ H-NMR (in CDCl ₃ ) δ7.51 (d, 4H), 7.43 (t, 2H), 7.36 (t, 4H), 2.14-2.21 (m, 8H).
Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-1) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 41%.

A desired iridium complex (A-50) was obtained in the same manner as in Example 2 except that the above dimer was used instead of the dimer used in Example 2. The isolation yield was 39%.

¹ H-NMR (in CDCl ₃ ) δ 7.76 (d, 4H), 7.51-7.57 (m, 6H), 7.22 (d, 2H), 6.69 (t, 2H), 6.58 (t, 2H), 6.44 ( d, 2H), 5.62 (s, 1H), 2.99-3.06 (m, 2H), 2.70-2.76 (m, 2H), 2.14-2.33 (m, 6H), 1.92-2.08 (m, 4H), 1.85 ( s, 6H), 1.63-1.68 (m, 2H).

ESI-MS (m/z):896 Example 12 (Synthesis of Compound (A-96) of the present invention)
A desired iridium complex (A-96) was obtained in the same manner as in Example 3 except that the dimer synthesized in Example 11 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 896

¹H-NMR (CDCl₃中)δ7.49 (d, 4H), 7.43 (t, 2H), 7.35 (t, 4H), 1.98 (m, 4H), 1.92 (m, 4H), 1.81 (m, 4H).
引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−３）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は３４％であった。

実施例２で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例２と同様の方法を用いて、所望のイリジウム錯体（Ａ−５４）を得た。単離収率は６６％であった。

¹H-NMR (CDCl₃中)δ7.75 (d, 4H), 7.52-7.58 (m, 6H), 7.17 (d, 2H), 6.65 (t, 2H), 6.55 (t, 2H), 6.50 (d, 2H), 5.69 (s, 1H), 2.80 (t, 2H), 2.66 (t, 2H), 2.09-2.25 (m, 4H), 1.97-2.04 (m, 2H), 1.81-1.93 (m, 12H), 1.72-1.76 (m, 2H), 1.58-1.66 (m, 4H), 1.16 (q, 2H). Example 13 (Synthesis of Compound (A-54) of the present invention)
The desired ligand (L-3) was obtained in the same manner as in Example 5, except that benzyl was used instead of 4,4′-difluorobenzyl and cycloheptanone was used instead of cyclohexanone. It was. The isolation yield was 98%.

¹ H-NMR (in CDCl ₃ ) δ 7.49 (d, 4H), 7.43 (t, 2H), 7.35 (t, 4H), 1.98 (m, 4H), 1.92 (m, 4H), 1.81 (m, 4H).
Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-3) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 34%.

A desired iridium complex (A-54) was obtained in the same manner as in Example 2 except that the above dimer was used instead of the dimer used in Example 2. The isolation yield was 66%.

¹ H-NMR (in CDCl ₃ ) δ 7.75 (d, 4H), 7.52-7.58 (m, 6H), 7.17 (d, 2H), 6.65 (t, 2H), 6.55 (t, 2H), 6.50 ( d, 2H), 5.69 (s, 1H), 2.80 (t, 2H), 2.66 (t, 2H), 2.09-2.25 (m, 4H), 1.97-2.04 (m, 2H), 1.81-1.93 (m, 12H), 1.72-1.76 (m, 2H), 1.58-1.66 (m, 4H), 1.16 (q, 2H).

ESI-MS (m/z):952 Example 14 (Synthesis of Compound (A-102) of the Present Invention)
A desired iridium complex (A-102) was obtained in the same manner as in Example 3, except that the dimer synthesized in Example 13 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 952

¹H-NMR (CDCl₃中)δ7.51 (d, 4H), 7.45 (t, 2H), 7.36 (t, 4H), 1.66 (s, 6H).
引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−２０）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は１０％であった。

実施例３で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例３と同様の方法を用いて、所望のイリジウム錯体（Ａ−１０５）を得た。

ESI-MS (m/z):844 Example 15 (Synthesis of the present compound (A-105))
The desired ligand (L-20) was obtained in the same manner as in Example 5 except that benzyl was used instead of 4,4′-difluorobenzyl and acetone was used instead of cyclohexanone. The isolation yield was 48%.

¹ H-NMR (in CDCl ₃ ) δ 7.51 (d, 4H), 7.45 (t, 2H), 7.36 (t, 4H), 1.66 (s, 6H).
Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-20) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 10%.

A desired iridium complex (A-105) was obtained in the same manner as in Example 3 except that the above dimer was used instead of the dimer used in Example 3.

ESI-MS (m / z): 844

¹H-NMR (CDCl₃中)δ7.79 (d, 4H), 7.53-7.60 (m, 6H), 7.28 (d, 2H), 6.69 (t, 2H), 6.59 (t, 2H), 6.51 (d, 2H), 5.65 (s, 1H), 1.98 (s, 6H), 1.85 (s, 6H), 1.69 (s, 6H). Example 16 (Synthesis of Compound (A-62) of the present invention)
The desired iridium complex (A) was prepared in the same manner as in Example 2 except that the dimer synthesized in Example 15 was used instead of the dimer used in Example 2 and the reaction time was further changed to 30 minutes. -62) was obtained. The isolation yield was 70%.

¹ H-NMR (in CDCl ₃ ) δ 7.79 (d, 4H), 7.53-7.60 (m, 6H), 7.28 (d, 2H), 6.69 (t, 2H), 6.59 (t, 2H), 6.51 ( d, 2H), 5.65 (s, 1H), 1.98 (s, 6H), 1.85 (s, 6H), 1.69 (s, 6H).

引き続き、２,３−ジフェニル−１,４−ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−２２）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は４８％であった。

実施例２で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例２と同様の方法を用いて、所望のイリジウム錯体（Ａ−６５）を得た。単離収率は５６％であった。

¹H-NMR (CDCl₃中)δ7.74 (d, 4H), 7.51-7.60 (m, 6H), 7.21 (d, 2H), 6.67 (t, 2H), 6.57 (t, 2H), 6.51 (d, 2H), 5.62 (s, 1H), 2.75 (m, 2H), 2.55 (m, 2H), 2.28 (m, 2H), 1.98 (m, 2H), 1.86 (s, 6H), 1.34 (t, 6H), 0.40 (t, 6H). Example 17 (Synthesis of Compound (A-65) of the present invention)
The desired ligand (L-22) was obtained in the same manner as in Example 5 except that benzyl was used instead of 4,4′-difluorobenzyl and 3-pentanone was used instead of cyclohexanone. It was. The isolation yield was 77%.

Subsequently, the same procedure as in Example 1 was conducted except that the above ligand (L-22) was used in place of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 48%.

A desired iridium complex (A-65) was obtained in the same manner as in Example 2 except that the above dimer was used instead of the dimer used in Example 2. The isolation yield was 56%.

¹ H-NMR (in CDCl ₃ ) δ 7.74 (d, 4H), 7.51-7.60 (m, 6H), 7.21 (d, 2H), 6.67 (t, 2H), 6.57 (t, 2H), 6.51 ( d, 2H), 5.62 (s, 1H), 2.75 (m, 2H), 2.55 (m, 2H), 2.28 (m, 2H), 1.98 (m, 2H), 1.86 (s, 6H), 1.34 (t , 6H), 0.40 (t, 6H).

ESI-MS (m/z):900 Example 18 (Synthesis of the present compound (A-104))
A desired iridium complex (A-104) was obtained in the same manner as in Example 3 except that the dimer synthesized in Example 17 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 900

ESI-MS (m/z):953 Example 19 (Synthesis of Compound (A-116) of the present invention)
The same as in Example 4 except that N-methyl-N- (pyridin-2-yl) pyridin-2-amine was used instead of 2,2′-dipyridylamine and the reaction time was further changed to 30 minutes. The desired iridium complex (A-116) was obtained using this method.

ESI-MS (m / z): 953

¹H-NMR (CDCl₃中)δ8.18 (d, 1H), 8.06 (t, 1H), 7.88 (d, 1H), 7.67-7.70 (m, 4H), 7.52-7.60 (m, 6H), 7.39 (t, 1H), 7.26 (d, 1H), 7.19 (d, 1H), 6.76-6.83 (m, 2H), 6.65-6.74 (m, 3H), 6.48 (d, 1H), 3.09 (dd, 1H), 2.59 (dd, 1H), 1.67-2.06 (m, 16H), 0.40 (m, 1H), 0.13 (d, 1H). Example 20 (Synthesis of Compound (A-70) of the present invention)
100 mg of the dimer synthesized in Example 1, 33 mg of pyridine-2-sulfonic acid, 67 mg of sodium carbonate, and 15 ml of 2-ethoxyethanol were placed in an eggplant flask and heated to reflux for 20 hours under an argon atmosphere. After the reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure to obtain a reddish brown solid. This reddish brown solid was recrystallized from methanol-water to obtain a desired iridium complex (A-70).

¹ H-NMR (in CDCl ₃ ) δ8.18 (d, 1H), 8.06 (t, 1H), 7.88 (d, 1H), 7.67-7.70 (m, 4H), 7.52-7.60 (m, 6H), 7.39 (t, 1H), 7.26 (d, 1H), 7.19 (d, 1H), 6.76-6.83 (m, 2H), 6.65-6.74 (m, 3H), 6.48 (d, 1H), 3.09 (dd, 1H), 2.59 (dd, 1H), 1.67-2.06 (m, 16H), 0.40 (m, 1H), 0.13 (d, 1H).

¹H-NMR (CDCl₃中)δ7.47 (d, 4H), 6.87 (d, 4H), 3.84 (s, 6H), 1.93-1.96 (m, 4H), 1.78 (brs, 4H), 1.72 (brs, 2H).
引き続き、２,３−ジフェニル−１,４-ジアザスピロ［４.５］デカ−１,３−ジエンの代わりに、上記配位子（Ｌ−６９）を用いた以外は、実施例１と同様の方法を用いて、中間体であるダイマーを得た。単離収率は４０％であった。

実施例２で用いたダイマーの代わりに、上記ダイマーを用いた以外は、実施例２と同様の方法を用いて、所望のイリジウム錯体（Ａ−５１）を得た。単離収率は５３％であった。

¹H-NMR (CDCl₃中)δ7.66 (d, 4H), 7.19 (d, 2H), 7.04 (d, 4H), 6.18 (d, 2H), 6.04 (s, 2H), 5.67 (s, 1H), 3.90 (s, 6H), 3.56 (s, 6H), 2.58-2.66 (m, 4H), 1.78-2.08 (m, 18H), 1.26 (brs, 2H), 1.08 (d, 2H). Example 21 (Synthesis of Compound (A-51) of the present invention)
The desired ligand (L-69) was obtained in the same manner as in Example 5 except that 4,4′-dimethoxybenzyl was used instead of 4,4′-difluorobenzyl. The isolation yield was 66%.

¹ H-NMR (in CDCl ₃ ) δ 7.47 (d, 4H), 6.87 (d, 4H), 3.84 (s, 6H), 1.93-1.96 (m, 4H), 1.78 (brs, 4H), 1.72 ( brs, 2H).
Subsequently, the same procedure as in Example 1 was conducted except that the above-mentioned ligand (L-69) was used instead of 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-diene. Using the method, an intermediate dimer was obtained. The isolation yield was 40%.

A desired iridium complex (A-51) was obtained using the same method as in Example 2 except that the above dimer was used instead of the dimer used in Example 2. The isolation yield was 53%.

¹ H-NMR (in CDCl ₃ ) δ7.66 (d, 4H), 7.19 (d, 2H), 7.04 (d, 4H), 6.18 (d, 2H), 6.04 (s, 2H), 5.67 (s, 1H), 3.90 (s, 6H), 3.56 (s, 6H), 2.58-2.66 (m, 4H), 1.78-2.08 (m, 18H), 1.26 (brs, 2H), 1.08 (d, 2H).

¹H-NMR (CDCl₃中)δ8.31 (d, 1H), 7.96 (t, 1H), 7.92 (d, 1H), 7.66 (d, 2H), 7.62 (d, 2H), 7.39 (t, 1H), 7.35 (d, 1H), 7.24 (d, 1H), 7.04 (d, 4H), 6.34 (d, 1H), 6.30 (s, 1H), 6.25 (d, 1H), 6.05 (s, 1H), 3.90 (s, 6H), 3.64 (s, 3H), 3.57 (s, 3H), 2.82 (dd, 1H), 1.22-1.97 (m, 17H), 0.29 (brs, 1H), 0.17 (s, 1H). Example 22 (Synthesis of Compound (A-28) of the present invention)
A desired iridium complex (A-28) was obtained in the same manner as in Example 1 except that the dimer synthesized in Example 21 was used instead of the dimer used in Example 1. The isolation yield was 89%.

¹ H-NMR (in CDCl ₃ ) δ 8.31 (d, 1H), 7.96 (t, 1H), 7.92 (d, 1H), 7.66 (d, 2H), 7.62 (d, 2H), 7.39 (t, 1H), 7.35 (d, 1H), 7.24 (d, 1H), 7.04 (d, 4H), 6.34 (d, 1H), 6.30 (s, 1H), 6.25 (d, 1H), 6.05 (s, 1H ), 3.90 (s, 6H), 3.64 (s, 3H), 3.57 (s, 3H), 2.82 (dd, 1H), 1.22-1.97 (m, 17H), 0.29 (brs, 1H), 0.17 (s, 1H).

ESI-MS (m/z):1044 Example 23 (Synthesis of the present compound (A-99))
A desired iridium complex (A-99) was obtained in the same manner as in Example 3 except that the dimer synthesized in Example 21 was used instead of the dimer used in Example 3.

ESI-MS (m / z): 1044

¹H-NMR (CDCl₃中)δ8.34 (d, 1H), 7.98 (t, 1H), 7.90 (d, 1H), 7.69-7.74 (m, 4H), 7.52-7.59 (m, 6H), 7.41 (dd, 1H), 7.35 (d, 1H), 7.25 (d, 1H), 6.72-6.84 (m, 3H), 6.64-6.68 (m, 2H), 6.42 (d, 1H), 3.13-3.17 (m, 1H), 1.75-2.36 (m, 11H), 1.41-1.49 (m, 1H), 1.13-1.19 (m, 2H), 0.82-0.90 (m, 1H). Example 24 (Synthesis of Compound (A-27) of the present invention)
A desired iridium complex (A-27) was obtained in the same manner as in Example 1 except that the dimer synthesized in Example 11 was used instead of the dimer used in Example 1. The isolation yield was 86%.

¹ H-NMR (in CDCl ₃ ) δ 8.34 (d, 1H), 7.98 (t, 1H), 7.90 (d, 1H), 7.69-7.74 (m, 4H), 7.52-7.59 (m, 6H), 7.41 (dd, 1H), 7.35 (d, 1H), 7.25 (d, 1H), 6.72-6.84 (m, 3H), 6.64-6.68 (m, 2H), 6.42 (d, 1H), 3.13-3.17 ( m, 1H), 1.75-2.36 (m, 11H), 1.41-1.49 (m, 1H), 1.13-1.19 (m, 2H), 0.82-0.90 (m, 1H).

Example 25 (Synthesis of the present compound (A-31))
A desired iridium complex (A-31) was obtained in the same manner as in Example 1 except that the dimer synthesized in Example 13 was used instead of the dimer used in Example 1. The isolation yield was 71%.

ESI-MS (m/z):948 Example 26 (Synthesis of Compound (A-127) of the present invention)
The desired iridium complex (A-127) was obtained using the same method as in Example 3, except that 1,10-phenanthroline was used instead of 2,2′-bipyridine. The isolation yield was 67%.

ESI-MS (m / z): 948

ESI-MS (m/z):952 Example 27 (Synthesis of the present compound (A-100))
The desired iridium complex (A-100) was obtained using the same method as in Example 3, except that 4,4′-dimethyl-2,2′-bipyridine was used instead of 2,2′-bipyridine. It was.

ESI-MS (m / z): 952

ESI-MS (m/z):1177 Example 28 (Synthesis of the present compound (A-101))
The desired iridium complex (A-101) was obtained using the same method as in Example 3 except that 4,4′-dinonyl-2,2′-bipyridine was used instead of 2,2′-bipyridine. It was.

ESI-MS (m / z): 1177

ESI-MS (m/z):984 Example 29 (Synthesis of Compound (A-106) of the present invention)
The desired iridium complex (A-106) was obtained using the same method as in Example 3 except that 4,4′-dimethoxy-2,2′-bipyridine was used instead of 2,2′-bipyridine. It was.

ESI-MS (m / z): 984

ESI-MS (m/z):983 Example 30 (Synthesis of the present compound (A-134))
The desired iridium complex (A-134) was obtained using the same method as in Example 3, except that 5-chloro-1,10-phenanthroline was used instead of 2,2′-bipyridine.

ESI-MS (m / z): 983

ESI-MS (m/z):963 Example 31 (Synthesis of Compound (A-133) of the Present Invention)
A desired iridium complex (A-133) was obtained in the same manner as in Example 3 except that 5-amino-1,10-phenanthroline was used instead of 2,2′-bipyridine.

ESI-MS (m / z): 963

  Next, the light emission characteristics of the compound of the present invention are shown below.

Example 32 (Luminescence of the present compound (A-24))
The compound (A-24) of the present invention was dissolved in THF and aerated with argon gas, and then the emission spectrum at room temperature (excitation) was measured using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (maximum emission wavelength: 632 nm). The emission quantum yield was 0.22.

Example 33 (Luminescence of the present compound (A-25))
The compound (A-25) of the present invention was dissolved in THF and aerated with argon gas, and then an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 615 nm). The emission quantum yield was 0.24.

Example 34 (Luminescence of the present compound (A-29))
The compound (A-29) of the present invention was dissolved in THF and aerated with argon gas, and then the emission spectrum at room temperature (excitation) was measured using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 629 nm). The emission quantum yield was 0.22.

Example 35 (Luminescence of the compound (A-47) of the present invention)
After the compound of the present invention (A-47) was dissolved in THF and argon gas was passed through, an emission spectrum (excitation) at room temperature was performed using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 646 nm). The emission quantum yield was 0.19.

Example 36 (Luminescence of the present compound (A-48))
The compound (A-48) of the present invention was dissolved in THF and aerated with argon gas, and then an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring apparatus (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 626 nm). The emission quantum yield was 0.28.

Example 37 (Luminescence of the present compound (A-52))
After the compound of the present invention (A-52) was dissolved in THF and argon gas was passed through, an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 646 nm). The emission quantum yield was 0.21.

Example 38 (Luminescence of the compound (A-50) of the present invention)
The compound (A-50) of the present invention was dissolved in THF and argon gas was passed through, and then an emission spectrum (excitation) at room temperature was performed using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 650 nm). The emission quantum yield was 0.16.

Example 39 (Luminescence of the present compound (A-54))
After the compound of the present invention (A-54) was dissolved in THF and argon gas was passed through, an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 655 nm). The emission quantum yield was 0.17.

Example 40 (Luminescence of the compound (A-65) of the present invention)
After the compound of the present invention (A-65) was dissolved in THF and argon gas was passed through, an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 652 nm). The emission quantum yield was 0.19.

Example 41 (Luminescence of the compound (A-127) of the present invention)
The compound (A-127) of the present invention was dissolved in THF and aerated with argon gas, and then the emission spectrum at room temperature (excitation) was measured using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 627 nm). The emission quantum yield was 0.19.

Example 42 (Luminescence of the present compound (A-134))
The compound of the present invention (A-134) was dissolved in THF and argon gas was passed through, and then an emission spectrum (excitation) at room temperature was performed using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (maximum emission wavelength: 625 nm). The emission quantum yield was 0.18.

Example 43 (Luminescence of the present compound (A-133))
The compound (A-133) of the present invention was dissolved in THF and aerated with argon gas, and then the emission spectrum at room temperature (excitation) was measured using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 640 nm). The emission quantum yield was 0.17.

Example 44 (Luminescence of the present compound (A-27))
The compound (A-27) of the present invention was dissolved in THF and argon gas was passed through, and then an emission spectrum (excitation) at room temperature was performed using an absolute PL quantum yield measuring apparatus (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 633 nm). The emission quantum yield was 0.21.

Example 45 (Emission of Compound (A-31) of the Present Invention)
After dissolving the compound (A-31) of the present invention in THF and venting with argon gas, an emission spectrum at room temperature (excitation) using an absolute PL quantum yield measuring apparatus (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 636 nm). The emission quantum yield was 0.14.

Example 46 (Luminescence of the present compound (A-28))
The compound (A-28) of the present invention was dissolved in THF and argon gas was passed through, and then an emission spectrum (excitation) at room temperature was performed using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 624 nm). The emission quantum yield was 0.19.

Example 47 (Luminescence of the present compound (A-51))
After the compound of the present invention (A-51) was dissolved in THF and argon gas was passed through, an emission spectrum (excitation) at room temperature using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. When the wavelength was measured, it showed strong red light emission (emission maximum wavelength: 635 nm). The emission quantum yield was 0.21.

Example 48 (Solid emission of the present compound (A-24))
When the absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. was used, the emission quantum yield (excitation wavelength: 330 nm) of the compound (A-24) in the room temperature solid state was measured. The emission quantum yield was 0.05.

Example 49 (Solid emission of the present compound (A-51))
When the absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd. was used, the emission quantum yield (excitation wavelength: 330 nm) of the compound (A-51) in the room temperature solid state was measured. The emission quantum yield was 0.11.

Example 50 (Solid emission of the compound (A-25) of the present invention)
Using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd., the emission quantum yield (excitation wavelength: 330 nm) of the compound (A-25) of the present invention in a room temperature solid state was measured. The emission quantum yield was 0.09.

Example 51 (Solid emission of the present compound (A-29))
Using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd., the emission quantum yield (excitation wavelength: 330 nm) of the compound (A-29) of the present invention in a room temperature solid state was measured. The emission quantum yield was 0.05.

Example 52 (Solid emission of the present compound (A-28))
Using an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd., the emission quantum yield (excitation wavelength: 330 nm) of the compound (A-28) in the room temperature solid state was measured. The emission quantum yield was 0.06.

Comparative Example 1
The tris (2-phenylpyridine) iridium complex described in Patent Document 1 exhibited green emission (maximum emission wavelength: 513 nm) in THF. In addition, using an absolute PL quantum yield measuring apparatus (C9920-02) manufactured by Hamamatsu Photonics Co., Ltd., the emission quantum yield (excitation wavelength: 330 nm) of the tris (2-phenylpyridine) iridium complex in the room temperature solid state is calculated. When measured, the emission quantum yield was 0.03.

  From the above examples, it was revealed that the metal coordination compound of the present invention represented by the general formula (1) or (2) exhibits excellent light emission characteristics in the visible light region (red region). Furthermore, it was revealed that the emission wavelength can be adjusted by introducing various substituents into the ligand of the metal coordination compound of the present invention and changing the ligand L. In addition, from Example 48 to Example 52, it was also revealed that the metal coordination compound of the present invention exhibits strong phosphorescence emission in a solid state as compared with the tris (2-phenylpyridine) iridium complex. Therefore, the metal coordination compound of the present invention is an organic electroluminescent element material, electrochemiluminescence (ECL) element material, luminescence sensor, photosensitizer, display, photographic material, laser dye, dye for color filter, optical communication It can be applied to color conversion filters, backlights, illumination, photosensitizing dyes, various light sources, and the like.

The emission spectrum of this invention compound (A-25) in THF at room temperature. The horizontal axis represents the wavelength, and the vertical axis represents the number of photons. The excitation wavelength is 350 nm. An emission spectrum of the compound (A-29) of the present invention in THF at room temperature. The horizontal axis represents the wavelength, and the vertical axis represents the number of photons. The excitation wavelength is 350 nm. An emission spectrum of the compound (A-48) of the present invention in THF at room temperature. The horizontal axis represents the wavelength, and the vertical axis represents the number of photons. The excitation wavelength is 350 nm. An emission spectrum of the compound (A-52) of the present invention in THF at room temperature. The horizontal axis represents the wavelength, and the vertical axis represents the number of photons. The excitation wavelength is 350 nm.

Claims (9)

A metal coordination compound represented by the following general formula (2).

(In General Formula (2), M represents iridium or platinum. N represents a nitrogen atom. M represents an integer of 1 to 3. n represents an integer of 0 to 2. m + n = 2 or 3. In R ¹ and R ² , R ¹ and R ² form a saturated carbocyclic ring having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or each independently represents a fluorine atom. R ^{3 to} R ¹¹ are each independently a hydrogen atom or a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and an optionally substituted alkyl group having 1 to 30 carbon atoms. 30 alkoxy groups, alkenyl groups having 2 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, cyano groups, amino groups having 0 to 30 carbon atoms, nitrogen having 1 to 30 carbon atoms, oxygen and / or Or a heterocyclic group containing a sulfur atom, 1 to 1 carbon atoms 0 acyl group, a hydroxyl group, or to the table a substituent selected from trifluoromethyl group, a hydrogen atom of the hydrocarbon moiety in these substituents may be substituted by a fluorine atom. In addition, R ³ ~ two groups adjacent R ⁷ and ^R 8 ^{to R 11} mAY form a naphthalene ring structure or a fluorene ring structure bonded to each other .Q is .k which represents a counter anion represents an integer of 0 to 2. L represents a bidentate ligand.) L is 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative 1-phenyl-1H-indazole derivative, 2-phenylbenzothiazole derivative, 2-phenylthiazole derivative, 2-phenylbenzoxazole derivative, 2-phenyloxazole derivative, 2-furanylpyridine derivative, 2- (2-benzofuranyl) Pyridine derivatives, 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 9- (2-pyridyl) cal Sol derivatives, 1- (2-pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) Quinoline derivatives, 3- (1-naphthyl) isoquinoline derivatives, 3- (2-naphthyl) isoquinoline derivatives, 2- (1-naphthyl) pyridine derivatives, 2- (2-naphthyl) pyridine derivatives, 6-phenylphenanthridine derivatives , 6- (1-naphthyl) phenanthridine derivative, 6- (2-naphthyl) phenanthridine derivative, benzo [c] acridine derivative, benzo [c] phenazine derivative, dibenzo [a, c] acridine derivative, dibenzo [ a, c] phenazine derivative, 2-phenylquinoxaline derivative, 2,3-diphenylquinoxaline derivative, 2- Selected from benzylpyridine derivatives, 2-phenylbenzimidazole derivatives, 3-phenylpyrazole derivatives, 4-phenylimidazole derivatives, 1-phenylimidazole derivatives, 4-phenyltriazole derivatives, 5-phenyltetrazole derivatives, or 2-alkenylpyridine derivatives. A bidentate ligand that forms an M-nitrogen bond and an M-carbon bond, a picolinic acid derivative, a pyridinesulfonic acid derivative, a quinolinesulfonic acid derivative, or a quinolinecarboxylic acid derivative, A bidentate ligand that forms an oxygen bond, a β-diketone derivative, a carboxylic acid derivative, a tropolone derivative, a bidentate ligand that forms two M-oxygen bonds, or a 2,2′-bipyridine derivative 1,10-phenanthroline derivatives, , 2'-biquinoline derivative, 2,2'-dipyridyl derivatives, imidazole derivatives, pyrazolyl borate derivative, selected from the pyrazole derivatives, according to claim 1 is a bidentate ligand which forms two of the M- nitrogen bond Metal coordination compounds. L is the metal coordination compound of Claim 1 or 2 represented by either of General formula (3)-(8).

(In General Formulas (3) to (8), R ^{12 to} R ⁴⁷ are each independently a hydrogen atom or a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, carbon Hetero that contains an alkenyl group having 2 to 30 atoms, an aryl group having 6 to 30 carbon atoms, a cyano group, an amino group having 0 to 30 carbon atoms, a nitrogen having 1 to 30 carbon atoms, an oxygen and / or a sulfur atom ring group, acyl group having 1 to 30 carbon atoms, a hydroxyl group, or to the table a substituent selected from trifluoromethyl group, a hydrogen atom of the hydrocarbon moiety in these substituents is substituted by a fluorine atom or. ^{Further, R 12 ~R 15, R 20} ~R 23, R 24 ~R 27, R 30 ~R 33 and two adjacent groups quinoline bonded to each other of ^R 34 ^{to R 37,} isoquinoline or Fe May form a Nantorijin ring structure, two groups adjacent to R ¹⁶ to R ¹⁹ is rather good also form a naphthalene ring structure bonded to each other, also, R ¹⁵ and R ^16, taken together benzo A quinoline ring structure or a dibenzoquinoline ring structure may be formed, and R ¹² and R ¹³ are bonded to each other, and at the same time, R ¹⁵ and R ¹⁶ are bonded to each other, whereby a benzoacridine ring structure or a dibenzoacridine ring structure is formed. It may form, also, R ³³ and R ³⁴ but it may also form a phenanthroline ring structure bonded to each other.) The metal coordination compound according to claim 1 , wherein m = 3 and n = 0. The metal coordination compound according to any one of claims 1 to 3, wherein m = 2 and n = 1. Metal coordination compound according to claims 1 to 5 or M is iridium. Luminescent material comprising a metal coordination compound according to 6 claim 1. A light emitting element using the light emitting material according to claim 7 . The intermediate body of the metal coordination compound in any one of Claim 1 to 6 represented by General formula (9).

In (formula (9), M is when .M is .N representing iridium or platinum represents a nitrogen atom of iridium is ^m 1 = 2, when M is platinum is ^m 1 = 1. R ¹ and R ² , R ¹ and R ² form a saturated carbocycle having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or each is independently substituted with a fluorine atom an alkyl group having 1 to 30 carbon atoms even if, ^R 3 ^{to R 11} each independently represents a hydrogen atom or a halogen atom, an alkyl group having 1 to 30 carbon atoms, 1-30 carbon atoms Alkoxy group, alkenyl group having 2 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, cyano group, amino group having 0 to 30 carbon atoms, nitrogen having 1 to 30 carbon atoms, oxygen and / or sulfur Heterocyclic group containing atoms, 1 to 3 carbon atoms 0 acyl group, a hydroxyl group, or to the table a substituent selected from trifluoromethyl group, a hydrogen atom of the hydrocarbon moiety in these substituents may be substituted by a fluorine atom. In addition, R ³ ~ two groups adjacent R ⁷ and ^R 8 ^{to R 11} mAY form a naphthalene ring structure or a fluorene ring structure bonded to each other .X represents a halogen atom.)

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