JP2009286716A - Iridium complex - Google Patents

Abstract

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、アミノ基、シアノ基、炭素数１〜１０のアルキル基またはアリール基を示し、これらは同一であっても異なっていてもよい。Ｒ^３は、水素原子、炭素数１〜１０のアルキル基または置換基を有していてもよいアリール基を示す。ｎは、２または３を示し、Ｌは、一価アニオンの二座配位子を示す。）で表されるイリジウム錯体。
【選択図】なし【Task】
Providing novel iridium complexes as phosphorescent materials.
[Solution]
Formula (1);
[Chemical 1]

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms or an aryl group, and these are the same. R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group which may have a substituent, n represents 2 or 3, and L represents Represents a bidentate ligand of a monovalent anion.).
[Selection figure] None

Description

  The present invention relates to an iridium complex that emits phosphorescence.

  In recent years, organic electroluminescence elements (organic EL elements) have attracted attention as next-generation display elements, and organic materials used for light-emitting elements have been vigorously developed. As the organic light emitting material, there are a fluorescent material using light emission from an excited singlet and a phosphorescent material using light emission from an excited triplet. In particular, phosphorescent materials have been vigorously developed. (See Non-Patent Document 1 and Non-Patent Document 2).

Most phosphorescent materials are metal complexes containing heavy atoms such as iridium and platinum, and many materials can be synthesized by a combination of a central metal and a ligand. For example, as an iridium complex as a phosphorescent material, many complexes in which a 5-membered ring structure is formed by a ligand and iridium have been proposed, such as Ir (ppy) ₃ coordinated with a phenylpyridine derivative ( Non-Patent Document 3 and Patent Document 1).
Jpn.H.Appl.Phys.Vol38.1502-1504 (1999) J. et al. Am. Chem. Soc. 2001, 123, 4304-4312 Inorg. Chem. 2001, 40, 1704-1711 Special table 2003-515897 gazette

  Applications of organic light-emitting materials are diversified today, and in order to respond to such demands, proposals for a wide variety of phosphorescent materials having different characteristics such as emission color are required.

  An object of the present invention is to provide a novel iridium complex as a phosphorescent material.

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、アミノ基、シアノ基、炭素数１〜１０のアルキル基またはアリール基を示し、これらは同一であっても異なっていてもよい。Ｒ^３は、水素原子、炭素数１〜１０のアルキル基または置換基を有していてもよいアリール基を示す。ｎは、２または３を示し、Ｌは、一価アニオンの二座配位子を示す。）で表されるイリジウム錯体。
項２． 式（１）におけるＲ^３で示される置換基を有していてもよいアリール基が、フェニル基である項１に記載のイリジウム錯体。 The present invention relates to an iridium complex as shown below.
Item 1. Formula (1);

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms or an aryl group, and these are the same. R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group which may have a substituent, n represents 2 or 3, and L represents Represents a bidentate ligand of a monovalent anion.).
Item 2. Item 4. The iridium complex according to item 1, wherein the aryl group optionally having a substituent represented by R ³ in formula (1) is a phenyl group.

  Hereinafter, the present invention will be described in detail.

式（１）中において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、アミノ基、シアノ基、炭素数１〜１０のアルキル基またはアリール基を示し、これらは同一であっても異なっていてもよい。Ｒ^３は、水素原子、炭素数１〜１０のアルキル基または置換基を有していてもよいアリール基を示す。ｎは、２または３を示し、Ｌは、一価アニオンの二座配位子を示す。
Ｒ^１およびＲ^２で示されるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子およびヨウ素原子等が挙げられる。
Ｒ^１およびＲ^２で示される炭素数１〜１０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｎ−オクチル基およびｎ−デシル基等が挙げられる。
Ｒ^１およびＲ^２で示されるアリール基としては、例えば、フェニル基、ナフチル基およびアントラセニル基等が挙げられる。
Ｒ^３で示される炭素数１〜１０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｎ−オクチル基およびｎ−デシル基等が挙げられる。
Ｒ^３で示される置換基を有していてもよいアリール基としては、例えば、フェニル基、３−メチルフェニル基、３−エチルフェニル基、３−ニトロフェニル基、３−アミノフェニル基、３−シアノフェニル基、４−メチルフェニル基、４−エチルフェニル基、４−ニトロフェニル基、４−アミノフェニル基、４−シアノフェニル基、ナフチル基、３−メチルナフチル基、３−エチルナフチル基、３−ニトロナフチル基、３−アミノナフチル基、３−シアノナフチル基、４−メチルナフチル基、４−エチルナフチル基、４−ニトロナフチル基、４−アミノナフチル基、４−シアノナフチル基、アントラセニル基、３−メチルアントラセニル基、３−エチルアントラセニル基、３−ニトロアントラセニル基、３−アミノアントラセニル基、３−シアノアントラセニル基、４−メチルアントラセニル基、４−エチルアントラセニル基、４−ニトロアントラセニル基、４−アミノアントラセニル基および４−シアノアントラセニル基等が挙げられ、中でも入手が容易で経済的である観点から、フェニル基が好適に用いられる。
Ｌで示される一価アニオンの二座配位子としては、特に制限されるものではないが、例えば、式（２）；

および式（３）；

で表される二座配位子等を挙げることができる。 The iridium complex of the present invention is represented by the following formula (1).

In Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an aryl group, They may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group which may have a substituent. n represents 2 or 3, and L represents a bidentate ligand of a monovalent anion.
Examples of the halogen atom represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples include a butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-octyl group and n-decyl group.
Examples of the aryl group represented by R ¹ and R ² include a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, Examples include n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-octyl group, and n-decyl group.
Examples of the aryl group which may have a substituent represented by R ³ include, for example, a phenyl group, a 3-methylphenyl group, a 3-ethylphenyl group, a 3-nitrophenyl group, a 3-aminophenyl group, 3- Cyanophenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-nitrophenyl group, 4-aminophenyl group, 4-cyanophenyl group, naphthyl group, 3-methylnaphthyl group, 3-ethylnaphthyl group, 3 -Nitronaphthyl group, 3-aminonaphthyl group, 3-cyanonaphthyl group, 4-methylnaphthyl group, 4-ethylnaphthyl group, 4-nitronaphthyl group, 4-aminonaphthyl group, 4-cyanonaphthyl group, anthracenyl group, 3-methylanthracenyl group, 3-ethylanthracenyl group, 3-nitroanthracenyl group, 3-aminoanthracenyl group, 3- Anoanthracenyl group, 4-methylanthracenyl group, 4-ethylanthracenyl group, 4-nitroanthracenyl group, 4-aminoanthracenyl group, 4-cyanoanthracenyl group, etc. Of these, a phenyl group is preferably used from the viewpoint of availability and economy.
Although it does not restrict | limit especially as a bidentate ligand of the monovalent anion shown by L, For example, Formula (2);

And formula (3);

The bidentate ligand etc. which are represented by these can be mentioned.

（式中、Ｒ^２は、上記式（１）におけるＲ^２と同じである。Ｘは、ハロゲン原子を示す。）で表されるピリジン化合物と式（５）；

（式中、Ｒ^１およびＲ^３は、それぞれ、上記式（１）におけるＲ^１およびＲ^３と同じである。）で表されるアミン化合物とをパラジウム触媒およびホスフィン触媒並びに塩基の存在下で反応させることにより、式（６）；

（式中、Ｒ^１およびＲ^３は、それぞれ、上記式（５）におけるＲ^１およびＲ^３と同じであり、Ｒ^２は、上記式（４）におけるＲ^２と同じである。）で表されるピリジルフェニルアミン化合物を得て、これと三塩化イリジウムの水和物とを反応させて式（７）；

で表されるμ−クロロダイマーとした後、さらにこれと、上記式（１）においてＬで示される一価アニオンの二座配位子を形成させるための式（８）；

で表されるアセチルアセトンまたは式（９）；

で表されるピリジンカルボン酸とを塩基性化合物の存在下で反応させることにより製造することができる。 In the formula (1) of the present invention, the iridium complex of n = 2 is, for example, the formula (4);

(Wherein R ² is the same as R ² in the above formula (1). X represents a halogen atom) and the formula (5);

(Wherein R ¹ and R ³ are the same as R ¹ and R ³ in the above formula (1), respectively) in the presence of a palladium catalyst, a phosphine catalyst and a base. By formula (6);

(Wherein, ^{R 1} and ^{R 3} are each the same as ^{R 1} and ^{R 3} in the formula (5), ^{R 2} is the same as ^{R 2} in the formula (4).) Expressed in A pyridylphenylamine compound is reacted with iridium trichloride hydrate to obtain a compound of formula (7);

And a formula (8) for forming a bidentate ligand of a monovalent anion represented by L in the above formula (1);

Or acetylacetone represented by the formula (9):

It can manufacture by making the pyridinecarboxylic acid represented by these react with presence of a basic compound.

  The iridium complex of formula (1) and n = 3 of the present invention can be produced by reacting the iridium complex of formula (1) and n = 2 with the compound of formula (6) in a nitrogen atmosphere. .

  In the above formula (4), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the pyridine compound represented by the above formula (4) include 2-chloropyridine, 2-bromopyridine, 2-iodopyridine, 2-chloro-4-methylpyridine, 2-chloro-4-bromo. Examples thereof include pyridine and 2-chloro-4-iodopyridine.

  Specific examples of the amine compound represented by the above formula (5) include diphenylamine and aniline.

  In the method for producing the pyridylphenylamine compound, commercially available pyridine compounds and amine compounds can be used.

  The amount of the amine compound used is preferably 1.0 to 2.0 mol, more preferably 1.0 to 1.5 mol, per 1 mol of the pyridine compound. When the usage-amount of an amine compound is less than 1.0 mol, there exists a possibility that reaction may not advance easily and reaction may become difficult to complete. Moreover, when the usage-amount of an amine compound exceeds 2.0 mol, there exists a possibility that it may not become economical without the effect corresponding to the usage-amount.

  Examples of the palladium catalyst include tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); palladium (II) chloride, palladium (II) bromide, palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (tri-o-tolylphosphine) Divalent palladium compounds such as palladium (II), dichlorotetraammine palladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroacetate; Nji) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) 0-valent palladium compounds such like. Among these, from the viewpoint of having high reaction activity, zero-valent palladium compounds are preferable, and tris (dibenzylideneacetone) dipalladium (0) is preferably used. These palladium catalysts may be used alone or in combination of two or more. The use ratio of the palladium catalyst is preferably 0.0001 to 0.2 mol, more preferably 0.0002 to 0.05 mol, relative to 1 mol of the pyridine compound. When the usage ratio of the palladium catalyst is less than 0.0001 mol, the reaction may not easily proceed. Moreover, when the usage-amount of a palladium catalyst exceeds 0.2 mol, there exists a possibility that it may not become economical without the effect corresponding to the usage-amount.

Examples of the phosphine catalyst include 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, 1,1′-bis (diphenylphosphino) ferrocene, N, N′-dimethyl-1- [ Phosphine compounds such as 1 ′, 2-bis (diphenylphosphino) ferrocenyl] and 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene. Among these, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl and 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene are preferable from the viewpoint of high reaction activity. Used for. These phosphine catalysts may be used alone or in combination of two or more. The use ratio of the phosphine catalyst is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, relative to 1 mol of the palladium catalyst. When the use ratio of the phosphine catalyst is less than 0.1 mol, the reaction may not easily proceed. Moreover, when the usage-amount of a phosphine catalyst exceeds 10 mol, there exists a possibility that it may not be economical without the effect corresponding to the usage-amount.
The base used in the reaction for obtaining the pyridylphenylamine compound is not particularly limited, and examples thereof include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium tert-butoxide and potassium tert. -Alkali metal alkoxides such as butoxide. In addition, you may use these bases individually or in combination of 2 or more types, respectively. The use ratio of the base is preferably 1 to 20 mol, and more preferably 1 to 10 mol, relative to 1 mol of the pyridine compound. When the use ratio of the base is less than 1 mol, the yield may be lowered, and when the use ratio of the base exceeds 20 mol, there is a possibility that the effect corresponding to the use amount may not be obtained and the economy may not be achieved.

  The solvent used in the reaction for obtaining the pyridylphenylamine compound is not particularly limited as long as it is an inert solvent for the reaction. For example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, diethyl ether, Examples include ether solvents such as tetrahydrofuran and dioxane; acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide and the like. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferably used because the solvent can be easily recycled. The amount of the solvent used is not particularly limited, but is 500 to 10,000 parts by weight with respect to 100 parts by weight of the pyridine compound from the viewpoint of facilitating the reaction and obtaining an effect corresponding to the amount of use. Is preferred.

  30-250 degreeC is preferable and, as for the temperature of reaction which obtains a pyridylphenylamine compound, 50-150 degreeC is more preferable. When the reaction temperature is lower than 30 ° C, the reaction may take a long time. Moreover, when reaction temperature is higher than 250 degreeC, there exists a possibility that a side reaction may occur and a yield may fall. Since the reaction time varies depending on the reaction temperature, it cannot be generally specified, but is usually 1 to 20 hours.

  The pyridylphenylamine compound thus obtained can be isolated by, for example, filtration and washing to remove the catalyst and the like, followed by recrystallization.

  The μ-chlorodimer can be produced by reacting the pyridylphenylamine compound obtained as described above with a hydrate of iridium trichloride.

  The use ratio of the pyridylphenylamine compound is preferably 2 to 4 mol, more preferably 2 to 3 mol, per 1 mol of iridium trichloride hydrate. When the usage ratio of the pyridylphenylamine compound is less than 2 mol, the yield may decrease, and when the usage ratio of the pyridylphenylamine compound exceeds 4 mol, there is a possibility that the effect is not suitable for the usage amount and it is not economical. is there.

  Examples of the solvent used in the reaction to obtain μ-chlorodimer include water, dimethylformamide, 1-methyl-2-pyrrolidone, dioxane, glycerol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, toluene, and chloroform. Can be mentioned. Among these, water and 2-ethoxyethanol are preferably used. In addition, you may use these solvents individually or in combination of 2 or more types. The amount of the solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining an effect sufficient to meet the amount used, 500 to 10,000 parts by weight with respect to 100 parts by weight of the pyridylphenylamine compound. It is preferable that

  The temperature of the reaction for obtaining the μ-chlorodimer is preferably 80 to 250 ° C., more preferably 100 to 250 ° C. When the reaction temperature is lower than 80 ° C., the reaction may take a long time. Moreover, when reaction temperature is higher than 250 degreeC, there exists a possibility that a yield may fall. Since the reaction time varies depending on the reaction temperature, it cannot be generally stated, but is usually 8 to 48 hours.

  The μ-chlorodimer can be isolated by a conventional method such as filtration or washing.

  The iridium complex having n = 2 in the formula (1) of the present invention is, for example, a μ-chlorodimer obtained as described above and acetylacetone or pyridinecarboxylic acid in a nitrogen atmosphere in the presence of a basic compound. It can be produced by reacting.

  The proportion of acetylacetone or pyridinecarboxylic acid used is preferably 2 to 4 mol, more preferably 2 to 3 mol, per mol of μ-chlorodimer. If the use ratio of acetylacetone or pyridinecarboxylic acid is less than 2 moles, the yield may decrease, and if the use ratio of acetylacetone or pyridinecarboxylic acid exceeds 4 moles, there is no effect corresponding to the use amount and it is not economical. There is a fear.

  Examples of the basic compound include potassium methoxide, sodium methoxide, t-butoxy potassium, t-butoxy sodium, potassium carbonate, sodium carbonate, triethylamine and the like.

  The use ratio of the basic compound is preferably 1 to 10 moles, more preferably 1 to 5 moles per mole of μ-chlorodimer. When the usage ratio of the basic compound is less than 1 mol, the yield may be reduced. Moreover, when the usage-amount of a basic compound exceeds 10 mol, there exists a possibility that it may not be economical without the effect corresponding to the usage-amount.

  Examples of the solvent used in the above reaction include dimethylformamide, 1-methyl-2-pyrrolidone, dioxane, glycerol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, toluene, and chloroform. The amount of the solvent used is not particularly limited, but is 500 to 10,000 parts by weight with respect to 100 parts by weight of μ-chlorodimer from the viewpoint of smoothing the reaction and obtaining an effect sufficient for the amount of use. Preferably there is.

  Although the temperature of the said reaction is not specifically limited, 50-250 degreeC is preferable and 80-250 degreeC is more preferable. When the reaction temperature is lower than 50 ° C., the reaction may take a long time. Moreover, when reaction temperature exceeds 250 degreeC, there exists a possibility that a yield may fall because a raw material decomposes | disassembles. Since the reaction time varies depending on the reaction temperature, it cannot be generally stated, but it is usually 6 to 48 hours.

  The iridium complex thus obtained can be isolated by conventional methods such as filtration and washing. The iridium complex can be purified by recrystallization, followed by silica gel column chromatography purification and, if necessary, sublimation purification.

  The iridium complex in which n = 3 in the formula (1) of the present invention is, for example, n = 3 in the formula (1) of the present invention obtained by reacting μ-chlorodimer with acetylacetone represented by the formula (8). It can manufacture by making the iridium complex of 2 and the pyridylphenylamine compound represented by Formula (6) react in nitrogen atmosphere.

  It is preferable that it is 1-3 mol with respect to the iridium complex of n = 2 in Formula (1), and, as for the usage-amount of a pyridylphenylamine compound, it is more preferable that it is 1-2 mol. If the use ratio of the pyridylphenylamine compound is less than 1 mol, the yield may decrease, and if the use ratio of the pyridylphenylamine compound exceeds 3 mol, there is a risk that the effect is not suitable for the use amount and it is not economical. is there.

  Examples of the solvent used in the above reaction include glycerol and ethylene glycol. The amount of the solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining an effect that is commensurate with the amount used, 100 parts by weight of the iridium complex with n = 2 in formula (1). It is preferably 500 to 10,000 parts by weight.

  Although the temperature of the said reaction is not specifically limited, 100-250 degreeC is preferable. When the reaction temperature is lower than 100 ° C., the reaction may take a long time. Moreover, when reaction temperature exceeds 250 degreeC, there exists a possibility that a yield may fall because a raw material decomposes | disassembles. Since the reaction time varies depending on the reaction temperature, it cannot be generally stated, but it is usually 6 to 48 hours.

  The iridium complex thus obtained can be isolated by, for example, filtration and washing to remove raw materials and the like and then recrystallization. The iridium complex can be purified by recrystallization, followed by silica gel column chromatography purification and, if necessary, sublimation purification.

  The iridium complex thus obtained can be used as a light emitting material for an organic EL device. A method for forming the light emitting layer of the organic EL element is not particularly limited, and methods such as an evaporation method, a coating method, and an ink jet method can be used. An organic EL element is an element in which a light emitting layer is formed between a pair of electrodes, an anode and a cathode, and may have layers such as a hole transport layer and an electron transport layer in addition to the light emitting layer.

  According to the present invention, a novel iridium complex as a phosphorescent material can be provided.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1] (In formula (1), R ¹ and R ² are hydrogen atoms, R ³ is a phenyl group, n is 2, and L is a bidentate represented by formula (2). Production of ligand iridium complex)

  A 300 mL four-necked flask equipped with a condenser, a thermometer and a stirrer was charged with 20.3 g (0.12 mol) of diphenylamine as an amine compound and 15.8 g (0.10 of 2-bromopyridine as a pyridine compound). Mol), tris (dibenzylideneacetone) dipalladium (0) 0.23 g (0.25 mmol), 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene 0.43 g (0.75 mmol) Sodium-tert-butoxide (10.6 g, 0.11 mol) and toluene (200 mL, 173.4 g). Subsequently, it heated up to 100 degreeC under nitrogen atmosphere, and also it was made to react by stirring at the same temperature for 5 hours. Then, 23.0 g (0.09 mol, yield 93.4%) of diphenyl-pyridin-2-yl-amine as a pyridylphenylamine compound was obtained by conventional methods such as filtration and washing.

  The obtained diphenyl-pyridin-2-yl-amine 2.22 g (9.0 mmol), iridium trichloride trihydrate 1.06 g (3.0 mmol), 2-ethoxyethanol 30 mL (27.9 g) And 10 mL (10.0 g) of water were charged into a 300 mL four-necked flask equipped with a condenser, thermometer and stirrer. Subsequently, after refluxing at 130 ° C. for 21 hours under a nitrogen atmosphere, 1.47 g (1.0 mmol, yield 68.1%) of μ-chlorodimer was obtained by a conventional method such as filtration and washing.

  1.47 g (1.0 mmol) of the obtained μ-chlorodimer, 0.3 g (3.0 mmol) of acetylacetone, 0.32 g (3.0 mmol) of sodium carbonate and 100 mL (93.0 g) of 2-ethoxyethanol Was charged into a 300 mL four-necked flask equipped with a condenser, a thermometer and a stirrer. Subsequently, after refluxing at 80 ° C. for 18 hours under a nitrogen atmosphere, 0.29 g (0.4 mmol, yield 74.0%) of iridium complex as yellow crystals was obtained by a conventional method such as filtration and washing.

The obtained yellow crystal is obtained by the formula (1) in which R ¹ and R ² are hydrogen atoms, R ³ is a phenyl group, n is 2, and L is represented by formula (2). It was confirmed by EI-MS analysis that it was an iridium complex as a bidentate ligand.

Molecular weight (calculated value): 782.22
Molecular weight (actual value): 782.22
m / e: 782.22 (100.0%), 780.22 (56.2%), 783.23 (42.5%), 781.22 (24.8%), 785.23 (9. 5%)

In addition, about the obtained yellow crystal, when the emission spectrum was measured with the fluorometer (Hitachi Ltd., brand name F-2500), it was (lambda) _max = 510nm.

[Example 2] (In the formula (1), R ¹ , R ² and R ³ are hydrogen atoms, n is 2, and L is a bidentate ligand represented by the formula (2). Complex production)

  In a 300 mL four-necked flask equipped with a condenser, a thermometer and a stirrer, 11.30 g (0.12 mol) of aniline as an amine compound and 15.8 g (0.10 of 2-bromopyridine as a pyridine compound) Mol), tris (dibenzylideneacetone) dipalladium (0) 0.23 g (0.25 mmol), 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene 0.43 g (0.75 mmol) Sodium-tert-butoxide (10.6 g, 0.11 mol) and toluene (200 mL, 173.4 g). Subsequently, it heated up to 100 degreeC under nitrogen atmosphere, and also it was made to react by stirring at the same temperature for 3 hours. Then, 15.8 g (0.09 mol, yield 92.9%) of phenyl-pyridin-2-yl-amine as a pyridylphenylamine compound was obtained by conventional methods such as filtration and washing.

  1.53 g (9.0 mmol) of the obtained phenyl-pyridin-2-yl-amine, 1.06 g (3.0 mmol) of iridium trichloride trihydrate, 30 mL of 2-ethoxyethanol (27.9 g) And 10 mL (10.0 g) of water were charged into a 300 mL four-necked flask equipped with a condenser, thermometer and stirrer. Subsequently, after refluxing at 130 ° C. for 15 hours under a nitrogen atmosphere, 1.13 g (1.0 mmol, yield 70.7%) of μ-chlorodimer was obtained by a conventional method such as filtration and washing.

  1.13 g (1.0 mmol) of the obtained μ-chlorodimer, 0.3 g (3.0 mmol) of acetylacetone, 0.32 g (3.0 mmol) of sodium carbonate and 100 mL (93.0 g) of 2-ethoxyethanol Was charged into a 300 mL four-necked flask equipped with a condenser, a thermometer and a stirrer. Next, after refluxing at 80 ° C. for 18 hours under a nitrogen atmosphere, the reaction solvent was distilled off under reduced pressure, and then 0.23 g (0.4 mmol, yield 73.0) of a yellow crystalline iridium complex by a conventional method such as filtration and washing. %).

The obtained yellow crystal is a bidentate ligand represented by the formula (1), wherein R ¹ , R ² and R ³ are hydrogen atoms, n is 2, and L is represented by the formula (2). It was confirmed by EI-MS analysis that it was a certain iridium complex.

Molecular weight (calculated value): 630.16
Molecular weight (actual value): 630.16
m / e: 630.16 (100.0%), 628.16 (59.2%), 631.16 (31.5%), 629.16 (18.9%), 632.17 (4. 5%)

In addition, about the obtained yellow crystal, when the emission spectrum was measured with the fluorometer (Hitachi Ltd., brand name F-2500), it was (lambda) _max = 400nm.

Claims (2)

Formula (1);

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms or an aryl group, and these are the same. R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group which may have a substituent, n represents 2 or 3, and L represents Represents a bidentate ligand of a monovalent anion.). The iridium complex according to claim 1, wherein the aryl group which may have a substituent represented by R ³ in formula (1) is a phenyl group.