JP6709487B2 - Iridium complex, and light emitting material and organic light emitting device using the compound - Google Patents

Description

The present invention relates to a novel iridium complex useful as a light emitting material for an organic light emitting device (organic electroluminescent device, organic electrochemiluminescent device, etc.) and an organic light emitting device using the compound.

In recent years, an organic light emitting device represented by an organic electroluminescent device has been attracting attention as a display or lighting technique, and research for practical use has been actively pursued. In particular, improvement of light emission efficiency is an important research subject, and as a light emitting material, attention is now focused on a phosphorescent material that utilizes light emission from an excited triplet state.

When the light emission from the excited singlet state is used, the generation ratio of the singlet excitons and the triplet excitons is 1:3, and thus the generation probability of the luminescent excitons is said to be 25%. Further, since the light extraction efficiency is about 20%, the limit of the external extraction quantum efficiency is set to 5%. On the other hand, if the excited triplet state can also be used for this, the upper limit of the internal quantum efficiency will be 100%, and therefore the emission efficiency will in principle be four times that of the case of the excited singlet. Against this background, phosphorescent materials have been actively developed so far.

For example, a 2-phenylpyrimidine iridium complex shown in Chemical formula 4 is disclosed (for example, see Patent Document 1). It is disclosed that this iridium complex emits green light, and that a green light emitting element can be manufactured by using the iridium complex.

Further, a blue light-emitting iridium complex in which a fluorine substituent is introduced into the phenyl group of the 2-phenylpyrimidine ligand shown in Chemical formula 5 is disclosed (see, for example, Patent Document 2).

Furthermore, as a compound similar to the present invention, a blue light-emitting pyrimidine iridium complex in which a fluorine substituent is introduced into a pyridine ring or a pyrimidine ring which is bonded to iridium shown in Chemical formula 6 at a carbon is disclosed (for example, Patent Document 3). See).

JP, 2009-40728, A International Publication No. 2011024747 Pamphlet JP 2012-19171 A JP, 2009-40728, A International publication 2011/024737 International Publication 2012/166608 International Publication No. 2010/056669 International Publication No. 2010/111755 International Publication 2012/158851

Inorg. Chem. , 2012, 51, 290-297. J. Flu. Chem. , 2009, 130, 640-649.

As described above, the conventionally known blue light-emitting pyrimidine iridium complex has a fluorine substituent introduced therein. However, it is known that fluorine is easily desorbed by heating an iridium complex having a fluorine substituent introduced therein (for example, Inorg. Chem., 2012, 51, 290-297. (Non-patent Document 1) and J. Flu. Chem., 2009, 130, 640-649. (Non-patent document 2)), and since there is a problem in thermal stability, development of a blue-emitting iridium complex that does not use a fluorine substituent. Is strongly desired.

An object of the present invention is to provide a novel iridium complex that can be applied to an organic electroluminescence device, an organic electrochemiluminescence device, and the like, and exhibits good emission characteristics in the visible light region (particularly in the blue region).

In view of the above situation, the present inventors have conducted extensive studies and found that the novel iridium complex represented by the general formula (1) exhibits strong light emission in the blue region. Then, by using the iridium complex of the present invention, it was demonstrated that a blue organic light emitting device exhibiting high luminous efficiency can be produced, and the present invention has been completed.

That is, according to this application, the following inventions are provided.

（一般式（１）中、Ｎは窒素原子を表す。Ｉｒはイリジウムを表す。ＸはＣ（Ｒ^６）または窒素原子を表す。Ｒ^１〜Ｒ^３は、各々独立に、水素原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アミノ基、アリールオキシ基、または、ハロゲン原子を表す。Ｒ^４〜Ｒ^６は、各々独立に、水素原子、アルキル基、アルコキシ基、または、アリールオキシ基を表す。但し、Ｒ^４とＲ^５の少なくとも１つが、アルキル基である。Ｒ ^４ 〜Ｒ ^６ のアルキル基、アルコキシ基、または、アリールオキシ基はフッ素で置換されることはない。ＸがＣ（Ｒ ^６ ）のときは、Ｒ ^４ とＲ ^５ とがアルキル基、または、Ｒ ^４ が水素原子でＲ ^５ がアルキル基であり、Ｘが窒素原子のときは、Ｒ ^４ が水素原子でＲ ^５ がアルキル基である。Ｒ^１とＲ^２、Ｒ^２とＲ^３は各々結合して環構造を形成してもよい。ｍ＝２〜３であり、ｎ＝０〜１であり、かつ、ｍ＋ｎ＝３である。Ｌはモノアニオン性２座配位子を表す。） The iridium complex according to the present invention is characterized by being represented by the following general formula (1).

(In the general formula (1), N represents a nitrogen atom, Ir represents iridium, X represents C(R ⁶ ), or a nitrogen atom. R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group. , An aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, R ^{4 to} R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group. Provided that at least one of R ⁴ and R ⁵ is an alkyl group, and the alkyl group, alkoxy group, or aryloxy group of R ^{4 to} R ⁶ is not substituted with fluorine. When (R ⁶ ), R ⁴ and R ⁵ are alkyl groups, or when R ⁴ is a hydrogen atom and R ⁵ is an alkyl group, and when X is a nitrogen atom, R ⁴ is a hydrogen atom and R ⁵ Is an alkyl group. R ¹ and R ² , and R ² and R ³ may be bonded to each other to form a ring structure, m= 2 to 3 , n= 0 to 1 and m+n. =3. L represents a monoanionic bidentate ligand.)

In the iridium complex according to the present invention, R ^{1 to} R ³ are preferably hydrogen atoms or alkyl groups.

In the iridium complex according to the present invention, R ⁴ and R ⁵ are preferably alkyl groups.

In the iridium complex according to the present invention, X is preferably C(R ⁶ ).

In the iridium complex according to the present invention, X is preferably a nitrogen atom.

In the iridium complex according to the present invention, L is preferably a nitrogen-containing heterocyclic ligand or a diketone ligand.

（一般式（２）〜（１０）中、Ｒ^７〜Ｒ^６４は、各々独立に、水素原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アミノ基、アリールオキシ基、または、ハロゲン原子を表す。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^２はＣ（Ｒ^７０）または窒素原子を表す。Ｒ^６５〜Ｒ^６７は、各々独立に、水素原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アミノ基、アリールオキシ基、または、ハロゲン原子を表す。Ｒ^６８〜Ｒ^７０は、各々独立に、水素原子、アルキル基、アルコキシ基、または、アリールオキシ基を表す。但し、Ｒ^６８とＲ^６９の少なくとも１つが、アルキル基、または、アルコキシ基である。Ｒ^６５とＲ^６６、Ｒ^６６とＲ^６７は各々結合して環構造を形成してもよい。） In the iridium complex according to the present invention, L is preferably at least one selected from general formulas (2) to (10).

(In formulas (2) to (10), R ^{7 to} R ⁶⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom. In addition, adjacent substituents may combine with each other to form a ring structure, X ² represents C(R ⁷⁰ ), or a nitrogen atom, and R ^{65 to} R ⁶⁷ each independently represent a hydrogen atom, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, and each of R ^{68 to} R ⁷⁰ independently represents a hydrogen atom, an alkyl group, an alkoxy group, or aryl. Represents an oxy group, provided that at least one of R ⁶⁸ and R ⁶⁹ is an alkyl group or an alkoxy group, R ⁶⁵ and R ⁶⁶ , and R ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring structure. Good.)

In the iridium complex according to the present invention, m is preferably 3.

In the iridium complex according to the present invention, it is preferable that m is 2 and n is 1.

The luminescent material according to the present invention is characterized by containing the iridium complex described in the present invention.

The organic light emitting device according to the present invention is characterized by including the light emitting material according to the present invention.

（一般式（１１）中、Ｎは窒素原子を表す。Ｉｒはイリジウムを表す。ＸはＣ（Ｒ^６）または窒素原子を表す。Ｙはハロゲン原子を表す。Ｒ^１〜Ｒ^３は、各々独立に、水素原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アミノ基、アリールオキシ基、または、ハロゲン原子を表す。Ｒ^４〜Ｒ^６は、各々独立に、水素原子、アルキル基、アルコキシ基、または、アリールオキシ基を表す。但し、Ｒ^４とＲ^５の少なくとも１つが、アルキル基である。Ｒ ^４ 〜Ｒ ^６ のアルキル基、アルコキシ基、または、アリールオキシ基はフッ素で置換されることはない。ＸがＣ（Ｒ ^６ ）のときは、Ｒ ^４ とＲ ^５ とがアルキル基、または、Ｒ ^４ が水素原子でＲ ^５ がアルキル基であり、Ｘが窒素原子のときは、Ｒ ^４ が水素原子でＲ ^５ がアルキル基である。Ｒ^１とＲ^２、Ｒ^２とＲ^３は各々結合して環構造を形成してもよい。） The compound according to the present invention is represented by the general formula (11).

(In the general formula (11), N represents a nitrogen atom, Ir represents iridium, X represents C(R ⁶ ) or a nitrogen atom, Y represents a halogen atom, and R ^{1 to} R ³ are each independently. Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, and R ^{4 to} R ⁶ are each independently a hydrogen atom, an alkyl group, or an alkoxy group. Represents a group or an aryloxy group, provided that at least one of R ⁴ and R ⁵ is an alkyl group, and the alkyl group, alkoxy group, or aryloxy group of R ^{4 to} R ⁶ is substituted with fluorine. When X is C(R ⁶ ), R ⁴ and R ⁵ are alkyl groups, or when R ⁴ is a hydrogen atom and R ⁵ is an alkyl group and X is a nitrogen atom, R is ⁴ is a hydrogen atom and R ⁵ is an alkyl group.R ¹ and R ² , and R ² and R ³ may combine with each other to form a ring structure.)

INDUSTRIAL APPLICABILITY The present invention can be applied to an organic electroluminescence device, an organic electrochemiluminescence device, and the like, and can provide an iridium complex having a novel structure that exhibits excellent emission characteristics in the visible light region (particularly in the blue region).

INDUSTRIAL APPLICABILITY The novel iridium complex of the present invention exhibits strong light emission mainly in the blue region at room temperature and is excellent in thermal stability, and thus can be suitably used as a light emitting element material for various applications. Further, an organic light-emitting device using the compound exhibits high-intensity light emission in the visible light region, and is therefore suitable for fields such as display devices, displays, backlights and illumination light sources.

3 is an emission spectrum of a compound of the present invention (Ir-53) in THF under an argon atmosphere. 3 is an emission spectrum of a compound of the present invention (Ir-59) in THF under an argon atmosphere. It is an emission spectrum of the co-deposition film (5:95 (mass% ratio)) of the compound of the present invention (Ir-53) and mCP. It is an emission spectrum of the co-deposition film (5:95 (mass% ratio)) of the compound of the present invention (Ir-59) and mCP. It is an EL spectrum of the organic electroluminescent element produced using this invention compound (Ir-59).

Next, the present invention will be described in detail by showing embodiments, but the present invention is not construed as being limited to these descriptions. The embodiments may be variously modified as long as the effects of the present invention are exhibited.

In the description of the general formula of the present invention, the hydrogen atom also includes an isotope (deuterium atom, etc.), and the atom constituting the substituent also includes that isotope.

The iridium complex according to the present invention is represented by the above general formula (1), and these iridium complexes are contained in a light emitting layer of an organic light emitting device or a plurality of organic compound layers including a light emitting layer by a vacuum deposition method, a spin coating method, or the like. Thus, an organic light emitting device that emits light in the visible light region (particularly in the blue region) can be obtained.

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

The iridium complex of the present invention is represented by the general formula (1), and a fluorine substituent is added to a substituent of a pyridine ring or a pyrimidine ring bonded to iridium with carbon (that is, R ^{4 to} R ⁶ in the general formula (1)). It has an advantageous feature that does not exist in the prior art that it emits light in the blue region without introducing it.

In the general formula (1), L is preferably at least one selected from the general formulas (2) to (10).

The compound of the present invention is represented by the general formula (11), and an iridium complex in which two molecules of ligand are coordinated per atom of iridium is crosslinked with a halogen atom to form a dimer. This compound is suitable as an intermediate substance when synthesizing the iridium complex according to the present invention.

Formula (1) symbols described to (11) will be described ^{(N, Ir, X, X} 2, m, n, L, Y, R 1 ~R 70) below.

In general formulas (1) to (11), N represents a nitrogen atom.

In general formulas (1) to (11), Ir represents iridium.

In formulas (1) to (11), X represents C(R ⁶ ) or a nitrogen atom.

In the general formula (1) ~ (11), X 2 represents C ^{(R 70)} or a nitrogen atom.

In general formulas (1) to (11), m is an integer of 1 to 3, n is an integer of 0 to 2, and m+n is 3. That is, when m is 3, n is 0, when m is 2, n is 1, and when m is 1, n is 2. Among these, a combination in which m is 3 and n is 0, and a combination in which m is 2 and n is 1 are more preferable.

In formulas (1) to (11), L represents a monoanionic bidentate ligand. Among the monoanionic bidentate ligands, a nitrogen-containing heterocyclic ligand or a diketone ligand is preferable.

Among the nitrogen-containing heterocyclic ligands, nitrogen-containing heterocyclic bidentate ligands are preferable, and examples thereof include 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 derivative, 7,8-benzoquinoline derivative, 7,8-benzoquinoxaline derivative, dibenzo[f,h]quinoline derivative, dibenzo[ f,h]quinoxaline derivative, benzo[h]-5,6-dihydroquinoline derivative, 9-(2-pyridyl)carbazole derivative, 1-(2-pyridyl)indole derivative, 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 Derivatives, benzo[c]acridine derivatives, benzo[c]phenazine derivatives, dibenzo[a,c]acridine derivatives, dibenzo[a,c]phenazine derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2- Benzylpyridine derivative, 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltriazole derivative, 5-phenyltetrazole derivative, 2-alkenylpyridine derivative, 5-phenyl -1,2,4-triazole derivative, imidazo[1,2-f]phenanthridine derivative, 1-phenylbenzimidazolium salt derivative, 1-phenylimidazolium salt derivative, picolinic acid derivative, pyridinesulfonic acid derivative, or , There is a pyrazabol derivative.

Among the diketone ligands, β-diketone ligands are preferable, and examples thereof include acetylacetone, 3-ethyl-2,4-pentanedione, 3,5-heptanedione, 3-butyl-2,4-pentanedione, 2, 6-Dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, 3-methyl-2,4-pentanedione, dipivaloylmethane and the like.

In formulas (1) to (11), Y represents a halogen atom. Among the halogen atoms, chlorine atom, bromine atom and iodine atom are preferable, and chlorine atom is more preferable.

R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom. A hydrogen atom, an alkyl group, an aryl group, an amino group or a halogen atom is preferable, and a hydrogen atom, an amino group or an alkyl group is more preferable. Particularly preferred is a hydrogen atom or an alkyl group. In addition, R ¹ and R ² , and R ² and R ³ may be bonded to each other to form a ring structure.

R ^{4 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group. However, at least one of R ⁴ and R ⁵ is an alkyl group or an alkoxy group. The alkyl group, alkoxy group or aryloxy group of R ^{4 to} R ⁶ is not substituted with fluorine. When X is C(R ⁶ ), it is preferable that R ⁴ and R ⁵ are alkyl groups, R ⁴ is a hydrogen atom and R ⁵ is an alkyl group, or R ⁴ and R ⁵ are alkoxy groups. When X is a nitrogen atom, it is preferable that R ⁴ is a hydrogen atom and R ⁵ is an alkyl group.

R ^{7 to} R ⁶⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom. Further, adjacent substituents may be bonded to each other to form a ring structure. R ^{7 to} R ⁶⁴ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a halogen atom, and more preferably a hydrogen atom, an alkyl group or an aryl group.

R ⁶⁵ has the same meaning as R ¹ and the desirable range is also the same. R ⁶⁶ has the same meaning as R ² and the desirable range is also the same. R ⁶⁷ has the same meaning as R ³ and the desirable range is also the same. R ⁶⁸ has the same meaning as R ⁴ and the desirable range is also the same. R ⁶⁹ has the same meaning as R ⁵ and the desirable range is also the same. R ⁷⁰ has the same meaning as R ⁶ and the desirable range is also the same.

When X ² is C(R ⁷⁰ ), R ⁶⁸ and R ⁶⁹ are preferably an alkyl group, R ⁶⁸ is a hydrogen atom and R ⁶⁹ is an alkyl group, or R ⁶⁸ and R ⁶⁹ are preferably an alkoxy group. .. When X is a nitrogen atom, R ⁶⁸ is preferably a hydrogen atom and R ⁶⁹ is preferably an alkyl group.

The alkyl group may be substituted with an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom.

The aryl group may be substituted with an alkyl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom.

The heterocyclic group may be substituted with an alkyl group, an aryl group, an alkoxy group, an amino group, an aryloxy group or a halogen atom.

The alkoxy group may be substituted with an alkyl group, an aryl group, a heterocyclic group, an amino group, an aryloxy group, or a halogen atom.

The amino group may be substituted with an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or a halogen atom.

The aryloxy group may be substituted with an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, or a halogen atom.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms. Most preferably, it is an alkyl group of the number 1 to 5.

Examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group. Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group Group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, or 3,5-tetramethylcyclohexyl group There is. Preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, or 1-methylpentyl group. More preferably, it is a methyl group or an ethyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms.

Examples of the aryl group include a phenyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a p-terphenyl-4-yl group, and a p-terphenyl-3-yl group. , P-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group , P-tolyl group, pt-butylphenyl group, p-(2-phenylpropyl)phenyl group, 4'-methylbiphenylyl group, 4"-t-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, mesityl group, m-quatphenyl group, 1-naphthyl group, or 2-naphthyl group, preferably phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, or mesityl group, especially alkyl. A phenyl group substituted with a group is particularly preferable because the sublimability of the iridium complex is improved.

The heterocyclic group is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably a heterocyclic group having 1 to 20 carbon atoms, and preferably a heterocyclic group having 1 to 10 carbon atoms. Particularly preferred is a heterocyclic group having 1 to 5 carbon atoms, and most preferred is a heterocyclic group.

Examples of the heterocyclic group include 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, 3-pyridazinyl group, 4- Pyridazinyl group, 5-pyridazinyl group, quinolinyl group, 1-pyrrolyl group, 1-imidazolyl group, 2-imidazopyridinyl group, 1-indolyl group, 2-benzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl Group, 1-isoquinolyl group, 1-phenanthridinyl group, 1-acridinyl group, 1-phenazinyl group, 2-thienyl group, 1-dibenzofuranyl group, 1,3,5-triazinyl group and the like. Of these, a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, and a 5-pyrimidyl group are preferable.

The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, and particularly preferably an alkoxy group having 1 to 10 carbon atoms. Most preferably, it is an alkoxy group of the number 1 to 5.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a t-butoxy group, and a methoxy group is preferable.

The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably an aryloxy group having 6 to 20 carbon atoms, and preferably an aryloxy group having 6 to 10 carbon atoms. Particularly preferred.

Examples of the aryloxy group include a phenoxy group and a naphthyloxy group, and a phenoxy group is preferable.

The halogen atom is preferably a chlorine atom, a bromine atom or a fluorine atom. A bromine atom or a fluorine atom is more preferable, and a bromine atom is particularly preferable.

R ¹ and R ² , and R ² and R ³ may be bonded to each other to form a ring structure. R ¹ and R ² , and R ² and R ³ are preferably bonded to each other to form a saturated or unsaturated 6-membered ring.

Of these, R ¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Of these, R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, or a tertiary butyl group, and more preferably a hydrogen atom, a methyl group, or It is an ethyl group.

Of these, R ⁴ and R ⁵ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, or a tertiary butyl group, and more preferably a hydrogen atom, a methyl group, or It is a tertiary butyl group.

Of these, R ⁶ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Of the above, an alkyl group is more preferable as R ⁷ and R ⁹ . Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, or a 1-methylpentyl group is A methyl group or a t-butyl group is more preferable, and a methyl group is particularly preferable.

As R ⁸ and R ^{10 to} R ²⁹ , a hydrogen atom or an alkyl group is more preferable among the above. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, 1-methylpentyl group, or A hydrogen atom is preferable, a methyl group or a hydrogen atom is particularly preferable, and a hydrogen atom is most preferable.

The ^{R 30 ~R 46, R 48 ~R} 50, R 52 ~R 56, R 58 ~R 64, a hydrogen atom among the above-mentioned alkyl group or aryl group, and more preferable. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, 1-methylpentyl group, phenyl Group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group A group, a 3,5-xylyl group, a mesityl group or a hydrogen atom is preferable, a methyl group or a hydrogen atom is particularly preferable, and a hydrogen atom is most preferable.

Of the above, R ⁴⁷ and R ⁵¹ are more preferably alkyl groups. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, or a 1-methylpentyl group is A methyl group or an isopropyl group is more preferable, and a methyl group is particularly preferable.

As R ⁵⁷ , a hydrogen atom or an aryl group is more preferable among the above. Specifically, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group A 3,4-xylyl group, a 3,5-xylyl group, a mesityl group or a hydrogen atom is preferable, and a 2,6-xylyl group or a mesityl group is particularly preferable.

R ⁶⁵ and R ⁶⁶ , and R ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring structure. R ⁶⁵ and R ⁶⁶ , and R ⁶⁶ and R ⁶⁷ are preferably bonded to each other to form a saturated or unsaturated 6-membered ring.

Of these, R ⁶⁵ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Of these, R ⁶⁶ and R ⁶⁷ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, or a tertiary butyl group, and more preferably a hydrogen atom, a methyl group, or It is an ethyl group.

Of these, R ⁶⁸ and R ⁶⁹ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, or a tertiary butyl group, and more preferably a hydrogen atom, a methyl group, or It is a tertiary butyl group.

Of these, R ⁷⁰ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Among the iridium complexes represented by the general formula (1) according to the present invention, the emission quantum yield in a solution or in a thin film state at room temperature is preferably 0.01 or more, and 0.1 or more. More preferably, it is particularly preferably 0.5 or more, and most preferably 0.7 or more.

In order to remove dissolved oxygen, the measurement of the luminescence quantum yield in the solution is performed after the solution in which the iridium complex is dissolved is bubbled with argon gas or nitrogen gas, or after the solution in which the luminescent material is dissolved is frozen and deaerated. Good to do. Either an absolute method or a relative method may be used as a method for measuring the emission quantum yield. In the relative method, the emission quantum yield can be measured by comparing the emission spectrum with a standard substance (quinine sulfate, etc.). In the absolute method, a commercially available device (for example, an absolute PL quantum yield measuring device (C9920-02) manufactured by Hamamatsu Photonics KK) can be used to measure the emission quantum yield in a solid state or in a solution. Is. The luminescence quantum yield in a solution can be measured using various solvents, but the iridium complex according to the present invention may be any one of the arbitrary solvents as long as the above luminescence quantum yield is achieved.

The emission quantum yield in a thin film state is measured, for example, by vacuum-depositing the iridium complex of the present invention on quartz glass and using a commercially available device (eg, absolute PL quantum yield measuring device (C9920, manufactured by Hamamatsu Photonics KK). ) Can be used. The emission quantum yield in a thin film can be measured by vapor-depositing the iridium complex of the present invention alone or co-evaporating with various host materials. It suffices if the yield is achieved.

The iridium complex represented by the general formula (1) according to the present invention mainly emits light in the visible light region (particularly in the blue region), but the wavelength region thereof depends on the type or structure of the ligand. Particularly, at room temperature, the maximum emission wavelength of the emission spectrum in a solution or in a thin film (when there are a plurality of emission maximum wavelengths, the emission maximum wavelength on the shortest wavelength side) is preferably in the range of 350 nm to 800 nm, and 400 nm. To 600 nm is more preferred, 450 nm to 550 nm is particularly preferred, 450 nm to 530 nm is more preferred, and 450 nm to 500 nm is most preferred.

Among the compounds represented by the general formula (1) according to the present invention, a particularly preferable iridium complex can be produced, for example, by any route of the formulas (A) to (O).

The case of m=3 and n=0 is, for example, the route of Expression (A).

The case of m=2 and n=1 is, for example, each route of Expressions (B) to (J).

The case of m=1 and n=2 is, for example, each route of Expressions (K) to (O).

Regarding the iridium complex represented by the general formula (1) according to the present invention, in addition to this, Japanese Patent Application Laid-Open No. 2009-40728 (Patent Document 4), International Publication No. 2011/024737 (Patent Document 5), and International Publication 2012/166608 (Patent Document 6), International Publication 2010/056669 (Patent Document 7), International Publication 2010/111755 (Patent Document 8), or International Publication 2012/158851 (Patent Document 9) It can be synthesized with reference to publicly known documents such as ).

The iridium complex represented by the general formula (1) according to the present invention can be used after purification according to a usual post-treatment of a synthetic reaction and, if necessary, with or without purification. As a method of the post-treatment, for example, extraction, cooling, crystallization by adding water or an organic solvent, or operation of distilling off the solvent from the reaction mixture 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.

Representative examples of the iridium complex represented by the general formula (1) according to the present invention are shown below in Tables 1 to 7, but the present invention is not limited thereto.

As described above, since the iridium complex represented by the general formula (1) according to the present invention can emit phosphorescence with high efficiency at room temperature, it can be used as a light emitting material or a light emitting substance of an organic light emitting element. Available. In addition, an organic light emitting device (preferably an organic electroluminescent device) can be produced using the light emitting material comprising the iridium complex of the present invention.

Further, by using the iridium complex represented by the general formula (1) according to the present invention, an organic light emitting element, a light emitting device, or a lighting device having high luminous efficiency can be realized. Further, an organic light emitting element, a light emitting device, or a lighting device with low power consumption can be realized.

Next, the organic electroluminescent element produced by using the iridium complex represented by the general formula (1) of the present invention will be described. The organic electroluminescent element is an element in which a plurality of layers of organic compounds are laminated between an anode and a cathode, and preferably contains an iridium complex represented by the general formula (1) as a light emitting material of the light emitting layer. The light emitting layer is generally composed of a light emitting material and a host material.

Typical element configurations of the organic electroluminescent element of the present invention include, for example, the following configurations, but the present invention is not limited thereto.
(1) Anode/light emitting layer/cathode (2) Anode/light emitting layer/electron transport layer/cathode (3) Anode/hole transport layer/light emitting layer/cathode (4) Anode/hole transport layer/light emitting layer/electron Transport layer/cathode (5) Anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (6) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode ( 7) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

A hole blocking layer (also referred to as a hole blocking layer) may be provided between the light emitting layer and the cathode. An electron blocking layer (also referred to as an electron barrier layer) may be provided between the light emitting layer and the anode.

Hereinafter, each layer constituting the organic electroluminescent element of the present invention will be described.

<Light emitting layer>
The light emitting layer is a layer in which electrons and holes injected from the electrode are recombined and emits light via excitons. Even if the light emitting portion is in the layer of the light emitting layer, the light emitting layer and the adjacent layer are May be the interface.

The thickness of the light emitting layer is preferably in the range of 2 nm to 1000 nm, more preferably in the range of 2 to 200 nm, and further preferably in the range of 3 to 150 nm.

In the present invention, the light emitting layer preferably contains a light emitting material and a host material.

As the light emitting material, the iridium complex represented by the general formula (1) according to the present invention may be contained alone or in combination, and other light emitting materials may be contained. Among the compounds contained in the light emitting layer, the total content of the iridium complex represented by the general formula (1) according to the present invention is preferably 1 to 50% by mass ratio, and 1 to 30%. Is more preferable, and 5 to 20% is particularly preferable.

Specific examples of the other light emitting material include anthracene derivative, pyrene derivative, chrysene derivative, fluoranthene derivative, perylene derivative, fluorene derivative, arylacetylene derivative, styrylarylene derivative, styrylamine derivative, arylamine derivative, boron complex, squarylium. Examples thereof include derivatives, oxobenzanthracene derivatives, fluorescein derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds, iridium complexes, and platinum complexes.

The host material is a compound mainly responsible for charge injection and transport in the light emitting layer. Further, among the compounds contained in the light emitting layer, the mass ratio in the layer is preferably 20% or more. It is more preferably 50% or more, and particularly preferably 80% or more. Among the compounds contained in the light emitting layer, the upper limit of the content of the host material is preferably 99% or less by mass ratio, more preferably 95% or less, and particularly preferably 90% or less. ..

The excited state energy (T ₁ level) of the host material is higher than the excited state energy (T ₁ level) of the iridium complex represented by the general formula (1) according to the present invention contained in the same layer. Is preferred.

A single host material or a plurality of host materials may be used. By using a plurality of host compounds, charge transfer can be adjusted and the efficiency of the organic electroluminescent device can be improved.

The host material that can be used in the present invention is not particularly limited, and may be a low molecular compound or a high molecular compound having a repeating unit.

Specific examples of the host material include triarylamine derivatives, phenylene derivatives, condensed ring aromatic compounds (for example, naphthalene derivatives, phenanthrene derivatives, fluorene derivatives, pyrene derivatives, tetracene derivatives, coronene derivatives, chrysene derivatives, perylene derivatives, 9, 10-diphenylanthracene derivative or rubrene, etc.), quinacridone derivative, acridone derivative, coumarin derivative, pyran derivative, Nile red, pyrazine derivative, benzimidazole derivative, benzothiazole derivative, benzoxazole derivative, stilbene derivative, organometallic complex (for example, tris Organic aluminum complex such as (8-quinolinolato)aluminum, organic beryllium complex, organic iridium complex, or organic platinum complex), or poly(phenylene vinylene) derivative, poly(fluorene) derivative, poly(phenylene) derivative, poly(thienylene) Examples thereof include high molecular weight derivatives such as renvinylene) derivatives and poly(acetylene) derivatives.

<Electron transport layer>
The electron transport layer is made of a material having a function of transporting electrons, and may have a function of transmitting the electrons injected from the cathode to the light emitting layer.

The thickness of the electron transport layer is not particularly limited, but is usually in the range of 2 nm to 5000 nm, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm.

The material used for the electron-transporting layer (hereinafter referred to as electron-transporting material) has only to have an electron injecting property or a transporting property or a hole blocking property. Any one can be selected and used.

Specific examples of the electron-transporting material include nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, organoaluminum complexes such as tris(8-quinolinolato)aluminum, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring). Is substituted with a nitrogen atom), pyridine derivative, pyrimidine derivative, triazine derivative, quinoline derivative, quinoxaline derivative, phenanthroline derivative, oxazole derivative, thiazole derivative, oxadiazole derivative, triazole derivative, benzimidazole derivative or benzoxazole derivative, etc. ), a dibenzofuran derivative, a dibenzothiophene derivative, or an aromatic hydrocarbon ring derivative (such as a naphthalene derivative, an anthracene derivative or triphenylene).

<Hole blocking layer>
The hole blocking layer is a layer having a function of an electron transporting layer in a broad sense, and is preferably made of a material having a function of transporting an electron and a small ability to transport a hole. Blocking the electrons can improve the recombination probability of electrons and holes.

The hole blocking layer is preferably provided adjacent to the cathode side of the light emitting layer.

The thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably 5 to 30 nm.

As the material used for the hole blocking layer, the material used for the electron transport layer described above is preferably used, and the host material described above is also preferably used for the hole blocking layer.

<Electron injection layer>
The electron-injection layer (also referred to as “cathode buffer layer”) is a layer provided between the cathode and the light-emitting layer in order to reduce the driving voltage or improve the emission luminance.

The thickness of the electron injection layer is preferably in the range of 0.1 to 5 nm. The range is more preferably 0.1 to 1 nm.

Specific examples of materials that are preferably used for the electron injection layer include metals (strontium or aluminum), alkali metal compounds (lithium fluoride, sodium fluoride, etc.), alkaline earth metal compounds (magnesium fluoride, calcium fluoride, etc.). Etc.), metal oxides (aluminum oxide, etc.), metal complexes (lithium 8-hydroxyquinolate (Liq), etc.) and the like. It is also possible to use the above-mentioned electron transport material. Further, examples of the electron injection material include a lithium complex of phenanthroline derivative (LiPB) and a lithium complex of phenoxypyridine (LiPP).

<Hole transport layer>
The hole transport layer is made of a material having a function of transporting holes, and may have a function of transmitting the holes injected from the anode to the light emitting layer. There may be a plurality of hole transport layers.

The film thickness of the hole transport layer is not particularly limited, but is usually in the range of 2 nm to 5000 nm, more preferably in the range of 5 to 500 nm, and further preferably in the range of 5 to 200 nm.

The material used for the hole-transporting layer (hereinafter referred to as the hole-transporting material) may have any of a hole-injecting property or a transporting property or an electron-blocking property, and is a conventionally known compound. Any of these can be selected and used.

As the hole transporting material, specifically, a porphyrin derivative; a phthalocyanine derivative; an oxazole derivative; a phenylenediamine derivative; a stilbene derivative; a triarylamine derivative; a carbazole derivative; an indolocarbazole derivative; an acene derivative such as anthracene or naphthalene; Fluorene derivative; Fluorenone derivative; Polymeric material or oligomer having polyvinylcarbazole or aromatic amine introduced in the main chain or side chain; Polysilane; Conductive polymer or oligomer (eg PEDOT:PSS, aniline copolymer, polyaniline, polythiophene, etc.) ) And the like.

<Electron blocking layer>
The electron blocking layer is a layer having a function of a hole transport layer in a broad sense, and is preferably made of a material having a function of transporting holes and having a small ability to transport electrons. By blocking the above, the recombination probability of electrons and holes can be improved.

The thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, more preferably 5 to 30 nm.

Further, the structure of the hole transport layer described above can be used as an electron blocking layer, if necessary.

<Hole injection layer>
In the present invention, the hole injection layer (also referred to as “anode buffer layer”) is a layer provided between the anode and the light emitting layer in order to reduce the driving voltage or improve the emission brightness.

Materials used for the hole injection layer include, for example, phthalocyanine derivatives represented by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides represented by vanadium oxide, amorphous carbon, polyaniline (emeraldine), polythiophene, and other conductive materials. Polymers, cyclometallated complexes represented by tris(2-phenylpyridine)iridium complex, triarylamine derivatives and the like are preferable.

The organic electroluminescent element of the present invention is preferably supported on a substrate. The material of the substrate is not particularly limited, and examples thereof include glass such as alkali glass, non-alkali glass or quartz glass, or transparent plastic, which is commonly used in conventional organic electroluminescent elements.

Specific examples of the material constituting the anode include simple metals such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, or tungsten, or alloys thereof; tin oxide, zinc oxide, indium oxide, oxidation. A metal oxide such as tin indium (ITO) or zinc indium oxide can be used. Also, a conductive polymer such as polyaniline, polypyrrole, polythiophene or polyphenylene sulfide can be used. These electrode substances may be used alone or in combination. The anode may be composed of a single layer or a plurality of layers.

Specific examples of the material forming the cathode include simple metals such as lithium, sodium, potassium, calcium, magnesium, aluminum, indium, ruthenium, titanium, manganese, yttrium, silver, lead, tin or chromium. Further, these metals may be combined to form an alloy. For example, alloys such as lithium-indium, sodium-potassium, magnesium-silver, aluminum-lithium, aluminum-magnesium, or magnesium-indium can be used. Further, a metal oxide such as indium tin oxide (ITO) can be used. These electrode substances may be used alone or in combination. The cathode may have a single layer structure or a multilayer structure.

The organic light-emitting device containing the iridium complex represented by the general formula (1) according to the present invention can be produced by a vacuum deposition method, a solution coating method, a transfer method using a laser or the like, or a spray method. In particular, it is desirable to form the light emitting layer containing the iridium complex represented by the general formula (1) according to the present invention by a vacuum vapor deposition method.

The vacuum deposition conditions for forming the respective layers such as the hole transport layer, the light emitting layer, and the electron transport layer by the vacuum deposition method are not particularly limited, but at a temperature of about 50 to 500° C. under a vacuum of about 10 ⁻⁴ to 10 ⁻⁵ Pa. It is preferable to deposit at a boat temperature of about -50 to 300° C. and a substrate temperature of about 0.01 to 50 nm/sec. When each layer such as the hole transport layer, the light emitting layer or the electron transport layer is formed by using a plurality of materials, it is preferable to co-evaporate the boats containing the materials while controlling the temperature of each boat.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The compounds corresponding to the examples are referred to as “invention compounds”, and the compounds corresponding to comparative examples are referred to as “comparative compounds”.

<Example I-1>
Synthesis of compound (Ir-4) of the present invention

Step 1 Synthesis of compound (A)

3.01 g of 3-bromo-2,6-dimethylpyridine, 4.30 g of bis(pinacolato)diboron, 3.34 g of potassium acetate, and 60 ml of dehydrated 1,4-dioxane were placed in a three-necked flask, and argon gas was bubbled through the flask. After that, [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct 0.391 g was added, and the mixture was heated and reacted at 100° C. for 17 hours in an argon atmosphere. After cooling the reaction solution to room temperature, 20 ml of 2M aqueous solution of tripotassium phosphate, 6 ml of ethanol, 2.90 g of 2-chloro-5-ethylpyrimidine, 0.370 g of tris(dibenzylideneacetone)dipalladium(0), and tri Phenylphosphine (0.676 g) was added, and the mixture was heated and reacted at 110° C. for 24 hours under an argon atmosphere. After the reaction solution was cooled to room temperature, it was filtered through Celite, and ethyl acetate was added to the obtained filtrate for extraction to collect an organic layer. This solution was concentrated under reduced pressure and purified using silica gel column chromatography (eluent: ethyl acetate and hexane) to obtain compound (A) in a yield of 74%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/Acetone-d ₆ ) δ: 8.76 (s, 2H), 8.14 (d, 1H), 7.16 (d, 1H), 2.72-2.76 (m , 5H), 2.49 (s, 3H), 1.31 (t, 3H).

Step 2 Synthesis of compound (B)

0.774 g of iridium trichloride n-hydrate, 1.30 g of compound (A), and 30 ml of DMF were placed in a flask, equipped with an arene condenser, and microwaved (2450 MHz, 700 W) for 30 minutes while aerating argon gas. Irradiated. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was collected and concentrated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (B) in a yield of 77%.

Step 3 Synthesis of (Ir-4)

0.314 g of the compound (B), 0.516 g of the compound (A), 0.314 g of potassium carbonate, and 3 ml of glycerin were placed in a three-necked flask, and heated and reacted at 150° C. for 14 hours under an argon atmosphere. After cooling the reaction solution to room temperature, dichloromethane and water were added for extraction. The organic layer was concentrated under reduced pressure and the precipitated solid was purified by silica gel column chromatography (eluent: ethyl acetate and dichloromethane) to obtain a meridional (Ir-4) in a yield of 35%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.67 (d, 1H), 8.58 (d, 2H), 8.04 (d, 1H), 7.84 (d, 1H), 7.53 (d, 1H), 6.59 (s, 1H), 6.23 (s, 1H), 6.08 (s, 1H), 2.93-2.96 (m, 9H), 2 .46-2.50 (m, 6H), 2.27-2.28 (m, 9H), 1.07-1.13 (m, 9H).

Step 4 Photoisomerization Reaction of Meridional Form (Ir-4) 0.5 mg of the compound (Ir-4) of the present invention, which is a meridional form, was dissolved in 0.75 ml of dichloromethane-d ₂ and placed in an NMR tube. This was irradiated with a UV lamp (wavelength: 365 nm) for 5 hours. ^When analyzed by ¹ H-NMR, it was found that the meridional form disappeared and photoisomerization was completed into the facial form (Ir-4). The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.73 (d, 1H), 7.44 (d, 1H), 6.54 (s, 1H), 3.00 (s, 3H), 2.52 (q, 2H), 2.29 (s, 3H), 1.13 (t, 3H).

<Example I-2>
Synthesis of compound of the present invention (Ir-38)

0.061 g of compound (B), 0.0364 g of sodium acetylacetonate, and 15 ml of 2-ethoxyethanol were placed in a three-necked flask, and heated under reflux for 15 hours under an argon atmosphere. The reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: dichloromethane and ethyl acetate) to obtain (Ir-38) in a yield of 53%. It was The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.75 (d, 2H), 8.46 (d, 2H), 5.99 (s, 2H), 5.33 (s, 1H), 2.93 (s, 6H), 2.75 (q, 4H), 2.22 (s, 6H), 1.82 (s, 6H), 1.33 (t, 6H).

<Example I-3>
Synthesis of compound of the present invention (Ir-52)

0.051 g of the compound (B), 0.033 g of sodium picolinate, and 15 ml of DMF were placed in a flask, an Aren condenser was attached, and microwaves (2450 MHz, 700 W) were irradiated for 30 minutes while aerating argon gas. The reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure, and water was added. The precipitated product was collected by filtration and purified by silica gel column chromatography (eluent: dichloromethane and methanol) to obtain (Ir-52) with a yield of 59%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/Acetone-d ₆ ) δ:8.71-8.75 (m, 3H), 8.27 (d, 1H), 7.98 (t, 1H), 7.75 (d. , 1H), 7.39-7.44 (m, 2H), 6.10 (s, 1H), 5.89 (s, 1H), 2.96 (s, 3H), 2.94 (s, 3H), 2.69 (q, 2H), 2.54 (q, 2H), 2.28 (s, 3H), 2.23 (s, 3H), 1.27 (t, 3H), 1. 13 (t, 3H).

<Example I-4>
Synthesis of compound of the present invention (Ir-60)

Compound (B) 0.072 g, pyridine-2-sulfonic acid 0.091 g, potassium carbonate 0.080 g, and DMF 20 ml were put in a flask, an Arene condenser was attached, and while microwaves (2450 MHz, while venting argon gas, (700 W) was irradiated for 30 minutes. After cooling the reaction solution to room temperature, the solvent was concentrated under reduced pressure and water was added. The precipitated product was collected by filtration and recrystallized using dichloromethane and hexane to obtain (Ir-60) in a yield of 47%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ )δ: 9.06 (s, 1H), 8.78 (t, 1H), 8.72 (s, 1H), 8.02-8.07 (m , 2H), 7.71 (s, 1H), 7.64 (d, 1H), 7.38 (t, 1H), 6.02 (s, 1H), 5.81 (s, 1H), 2 .96 (s, 3H), 2.92 (s, 3H), 2.73 (q, 2H), 2.60 (q, 2H), 2.27 (s, 3H), 2.21 (s, 3H), 1.30 (t, 3H), 1.18 (t, 3H).

<Example I-5>
Synthesis of the compound of the present invention (Ir-67)

0.309 g of compound (B), 0.128 g of silver trifluoromethanesulfonate, 5 ml of methanol, and 10 ml of dichloromethane were placed in a three-necked flask, and heated and reacted at 50° C. for 5 hours under an argon atmosphere. The reaction solution was cooled to room temperature, filtered through Celite, and the solvent was evaporated under reduced pressure. 2-phenyl pyridine 0.104g, methanol 5ml, and ethanol 10ml were added here, and it was made to heat-react at 80 degreeC for 24 hours under argon atmosphere. After the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure. This was purified using silica gel column chromatography (eluent: dichloromethane and methanol) to obtain a meridional (Ir-67) in a yield of 70%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.54 (t, 2H), 8.05 (d, 1H), 7.98 (d, 1H), 7.85 (t, 1H), 7.78 (d, 1H), 7.70-7.75 (m, 1H), 7.60 (d, 1H), 6.96-7.04 (m, 3H), 6.82 (dd, 1H), 6.31 (s, 1H), 6.17 (s, 1H), 2.98 (s, 3H), 2.94 (s, 3H), 2.38-2.51 (m, 4H). ), 2.30-2.30 (m, 6H), 1.08 (t, 3H), 1.02 (t, 3H).

Step 2 Photoisomerization Reaction of Meridional Form (Ir-67) 0.5 mg of the compound (Ir-67) of the present invention, which is a meridional form, was dissolved in 0.75 ml of dichloromethane-d ₂ and placed in an NMR tube. This was irradiated with a UV lamp (wavelength: 365 nm) for 7 hours. ^{As a result of 1} H-NMR analysis, it was found that the meridional form disappeared and the photoisomer was completely converted to the facial form (Ir-67). The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.72 (d, 1H), 8.68 (d, 1H), 7.98 (d, 1H), 7.71-7.76 (m , 2H), 7.54 (d, 1H), 7.44-7.47 (m, 2H), 6.97-7.00 (m, 2H), 6.86 (t, 1H), 6. 70 (t, 1H), 6.58 (s, 2H), 3.00 (s, 3H), 2.98 (s, 3H), 2.48-2.54 (m, 4H), 2.27. (S, 3H), 2.25 (s, 3H), 1.15 (t, 3H), 1.09 (t, 3H).

<Example I-6>
Synthesis of the compound of the present invention (Ir-42)

Step 1 Synthesis of compound (C)

5-Bromo-2-methylpyridine (3.09 g), bis(pinacolato)diboron (4.87 g), potassium acetate (5.64 g), and dehydrated 1,4-dioxane (100 ml) were placed in a three-necked flask, and an argon gas was passed through the flask. 1,1′-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride 0.213 g of a dichloromethane adduct was added, and the mixture was heated and reacted at 100° C. for 20 hours under an argon atmosphere. After cooling the reaction solution to room temperature, 40 ml of a 2M aqueous solution of tripotassium phosphate, 40 ml of toluene, 2.44 g of 2-chloro-5-ethylpyrimidine, 0.407 g of tris(dibenzylideneacetone)dipalladium(0), and 0.744 g of triphenylphosphine was added, and the mixture was heated and reacted at 110° C. for 17 hours in an argon atmosphere. The reaction solution was cooled to room temperature and then filtered through Celite, ethyl acetate was added to the filtrate for extraction, and the organic layer was collected. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (eluent: ethyl acetate), and further distilled under reduced pressure to obtain the compound (C) in a yield of 82%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 9.49 (d, 1 H), 8.64 (s, 2 H), 8.54 (dd, 1 H), 7.26 (d, 1 H), 2. 69 (q, 2H), 2.63 (s, 3H), 1.32 (t, 3H).

Step 2 Synthesis of compound (D)

0.271 g of iridium trichloride n hydrate, 0.301 g of compound (C), 15 ml of DMF, and 0.271 g of potassium carbonate were placed in a flask, and an Aren condenser was attached to the flask. , 700 W) for 30 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained product was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was recovered and the solvent was evaporated under reduced pressure. The obtained solid was recrystallized using dichloromethane and hexane to obtain the compound (D) in a yield of 67%.

Step 3 Synthesis of (Ir-42)

0.159 g of compound (D), 0.147 g of acetylacetone, 0.313 g of potassium carbonate, and 20 ml of DMF were put in a flask, equipped with an Arene condenser, and microwaved (2450 MHz, 700 W) for 30 minutes while aerating argon gas. Irradiated. After the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure and water was added. The precipitated product was collected by filtration and recrystallized using dichloromethane and hexane. Further purification was performed using silica gel column chromatography (eluent: ethyl acetate and methanol) to obtain (Ir-42) in a yield of 5%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/acetone-d ₆ )δ: 8.84 (d, 2H), 8.73 (s, 2H), 8.55 (d, 2H), 6.20 (s, 2H), 5.36 (s, 1H), 2.83 (q, 4H), 2.18 (s, 6H), 1.77 (s, 6H), 1.33 (t, 6H).

<Example I-7>
Synthesis of compound of the present invention (Ir-53)

0.20 g of compound (D), 0.20 g of picolinic acid, 0.22 g of potassium carbonate, and 40 ml of DMF were put in a flask, equipped with an arene condenser, and microwave (2450 MHz, 700 W) was applied to the flask while aerating argon gas. Irradiated for minutes. The reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure, and water was added. The precipitated product was collected by filtration and purified by silica gel column chromatography (eluent: dichloromethane and methanol) to obtain (Ir-53) in a yield of 45%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ CL ₂ ) δ: 8.87 (d, 2H), 8.74 (d, 1H), 8.69 (dd, 2H), 8.30 (d, 1H), 8.01 (t, 1H), 7.80 (d, 1H), 7.45-7.49 (m, 1H), 7.34 (d, 1H), 6.31 (s, 1H), 6 .17 (s, 1H), 2.72 (q, 2H), 2.56 (q, 2H), 2.38 (s, 3H), 2.36 (s, 3H), 1.29 (t, 3H), 1.14 (t, 3H).

<Example I-8>
Synthesis of the compound of the present invention (Ir-47)

Step 1 Synthesis of compound (E)

3.67 g of 5-bromo-2-tert-butylpyrimidine, 4.54 g of bis(pinacolato)diboron, 5.36 g of potassium acetate, and 100 ml of dehydrated 1,4-dioxane were placed in a three-necked flask, and then argon gas was bubbled. [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride 0.263 g of a dichloromethane adduct was added, and the mixture was heated and reacted at 100° C. for 17 hours in an argon atmosphere. After the reaction solution was cooled to room temperature, 30 mL of a 2 M aqueous solution of tripotassium phosphate, 20 mL of toluene, 2.32 g of 2-chloro-4-methylpyrimidine, and 0.314 g of tetrakistriphenylphosphine palladium (0) were added, and an argon atmosphere was added. The mixture was heated at 110° C. for 24 hours under heating. The reaction solution was cooled to room temperature, filtered through Celite, and ethyl acetate was added to the filtrate for extraction. The product obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (eluent: ethyl acetate and hexane) to obtain the compound (E) in a yield of 87%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 9.60 (s, 2H), 8.65 (d, 1H), 7.11 (d, 1H), 2.59 (s, 3H), 1. 47 (s, 9H).

Step 2 Synthesis of compound (F)

0.071 g of iridium trichloride n hydrate, 0.10 g of compound (E), 0.060 g of potassium carbonate, and 20 ml of DMF were placed in a flask, an Arene condenser was attached, and while microwaves (2450 MHz , 700 W) for 3 minutes. After cooling to room temperature, 0.136 g of potassium carbonate was added, and microwaves (2450 MHz, 700 W) were irradiated for 30 minutes while aerating argon gas. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was collected and concentrated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (F) in a yield of 67%.

Step 3 Synthesis of (Ir-47)

0.739 g of compound (F), 0.535 g of acetylacetone, 0.731 g of potassium carbonate, and 80 ml of DMF were placed in a flask, equipped with an Aren condenser, and microwaved (2450 MHz, 700 W) for 40 minutes while aerating argon gas. Irradiated. After cooling the reaction solution to room temperature, the solvent was concentrated under reduced pressure and water was added. The precipitated product was collected by filtration and recrystallized using dichloromethane and hexane. Further purification was carried out using silica gel column chromatography (eluent: ethyl acetate and hexane) to obtain (Ir-47) with a yield of 40%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/acetone-d ₆ )δ: 8.65 (d, 2H), 8.55 (s, 2H), 7.43 (d, 2H), 5.35 (s, 1H), 2.76 (s, 6H), 1.80 (s, 6H), 1.06 (s, 18H).

<Example I-9>
Synthesis of compound of the present invention (Ir-49)

0.1533 g of compound (F), 0.0615 g of silver trifluoromethanesulfonate, 5 ml of acetonitrile and 10 ml of dichloromethane were placed in a three-necked flask and stirred at 50° C. for 3 hours. The reaction solution was cooled to room temperature and filtered through Celite. The filtrate was concentrated under reduced pressure. To this, 0.0456 g of trifluoroacetylacetone, 0.1356 g of potassium carbonate, and 10 ml of ethanol were put, and the mixture was heated and reacted at 50° C. for 5 hours in an argon gas atmosphere. The solvent was concentrated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: ethyl acetate and dichloromethane) to obtain (Ir-49) in a yield of 18%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.57 (s, 2H), 8.42 (d, 1H), 8.40 (d, 1H), 7.18 (d, 1H), 7.16 (d, 1H), 5.72 (s, 1H), 2.76 (s, 6H), 2.01 (s, 3H), 1.07 (s, 18H).

<Example I-10>
Synthesis of the compound of the present invention (Ir-59)

0.61 g of compound (F), 0.60 g of picolinic acid, 0.60 g of potassium carbonate, and 100 ml of DMF were put in a flask, equipped with an Arene condenser, and microwaved (2450 MHz, 700 W) at 30 while aerating argon gas. Irradiated for minutes. The reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure, and water was added. The precipitated product was collected by filtration and purified by silica gel column chromatography (eluent: dichloromethane and methanol) to obtain (Ir-59) in a yield of 45%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ:8.66-8.72 (m, 3H), 8.29 (d, 1H), 7.99 (dd, 1H), 7.83 (d. , 1H), 7.63 (d, 1H), 7.48 (dd, 1H), 7.14 (d, 1H), 6.97 (d, 1H), 2.71 (s, 3H), 2 .70 (s, 3H), 1.15 (s, 9H), 1.10 (s, 9H).

<Example I-11>
Synthesis of the compound of the present invention (Ir-22)

0.101 g of iridium acetate (manufactured by ChemPur GmbH), 0.3722 g of compound (E), and 20 ml of diethylene glycol were placed in a three-necked flask, and heated and reacted at 235° C. for 12 hours under an argon atmosphere. After cooling the reaction solution to room temperature, the obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, and then the organic layer was collected and concentrated under reduced pressure. This was purified using silica gel column chromatography (eluent: ethyl acetate and hexane) to obtain a meridional (Ir-22) in a yield of 15%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ:8.87 (s,1H),8.81 (s,1H),8.65 (s,1H),8.14 (d,1H), 7.88 (d, 1H), 7.75 (d, 1H), 6.97 (d, 1H), 6.85 (d, 1H), 6.82 (d, 1H), 2.63 (s , 3H), 2.61 (s, 6H), 1.26 (s, 9H), 1.18 (s, 18H).

<Example I-12>
Synthesis of compound of the present invention (Ir-48)

Step 1 Synthesis of compound (G)

5.87 g of 5-bromo-2-tert-butylpyrimidine, 5.48 g of bis(pinacolato)diboron, 2.11 g of potassium acetate, and 50 ml of dehydrated 1,4-dioxane were put into a three-necked flask, and after aeration with argon gas , [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct 0.602 g was added, and the mixture was heated and reacted at 110° C. for 5 hours in an argon atmosphere. After cooling to room temperature and filtration with Celite, the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography (eluent: ethyl acetate and hexane) to obtain 2.68 g of a reaction intermediate. This reaction intermediate 2.68 g, 2 M aqueous solution of tripotassium phosphate 20 mL, toluene 30 mL, ethanol 10 mL, and 2-chloro-5-ethylpyrimidine 1.29 g were placed in a three-necked flask, and argon gas was bubbled for 30 minutes, followed by tetrakistri. 0.588 g of phenylphosphine palladium (0) was added, and the mixture was heated and reacted at 110° C. for 24 hours in an argon atmosphere. The reaction solution was cooled to room temperature, filtered through Celite, and ethyl acetate was added to the filtrate for extraction. The product obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (eluent: dichloromethane and ethyl acetate) to obtain the compound (G) in a yield of 73%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 9.57 (s, 2H), 8.69 (s, 2H), 2.71 (q, 2H), 1.46 (s, 3H), 1.32 (t, 9H).

Step 2 Synthesis of compound (H)

0.877 g of iridium trichloride n hydrate, 1.20 g of compound (G), and 50 ml of DMF were placed in a flask, equipped with an arene condenser, and microwaved (2450 MHz, 700 W) for 30 minutes while aerating argon gas. Irradiated. After further cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was collected and concentrated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (H) in a yield of 77%.

Step 3 Synthesis of (Ir-48)

0.120 g of compound (H), 0.0414 g of sodium acetylacetonate, and 15 ml of 2-ethoxyethanol were put into a three-necked flask, and heated and reacted at 120° C. for 17 hours under an argon atmosphere. After cooling the reaction solution to room temperature, the reaction solution was concentrated, water was added, and the precipitate was collected by filtration. This was purified using silica gel column chromatography (eluent: dichloromethane and ethyl acetate) to obtain (Ir-48) in a yield of 60%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/acetone-d ₆ )δ: 8.85 (d, 2H), 8.67 (d, 2H), 8.53 (s, 2H), 5.36 (s, 1H), 2.85 (q, 4H), 1.35 (t, 6H), 1.81 (s, 6H), 1.05 (s, 18H).

<Example I-13>
Synthesis of compound of the present invention (Ir-56)

0.100 g of compound (H), 10 ml of acetonitrile, and 0.0381 g of silver trifluoromethanesulfonate were placed in a three-necked flask, and heated and reacted at 50° C. for 3 hours under an argon atmosphere. The reaction solution was cooled to room temperature, filtered through Celite, and the filtrate was concentrated under reduced pressure. To this, 0.0422 g of sodium picolinate and 10 ml of acetonitrile were added, and the mixture was heated under reflux for 5 hours under an argon atmosphere. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was purified using silica gel column chromatography (eluent: dichloromethane and methanol) to obtain (Ir-56) in a yield of 19%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ ) δ: 8.77 (d, 1H), 8.64-8.67 (m, 4H), 8.31 (d, 1H), 8.01 (dd). , 1H), 7.82 (d, 1H), 7.61 (d, 1H), 7.49 (dd, 1H), 2.72 (q, 2H), 2.52-2.60 (m, 2H), 1.32 (t, 3H), 1.17 (t, 3H), 1.14 (s, 9H), 1.08 (s, 9H).

<Example I-14>
Synthesis of compound of the present invention (Ir-61)

Compound (H) 0.061 g, pyridine-2-sulfonic acid 0.0265 g, sodium carbonate 0.0158 g, and DMF 15 ml were placed in a flask, an Aren condenser was attached, and microwaves (2450 MHz, while venting an argon gas, (700 W) was irradiated for 30 minutes. The reaction solution was cooled to room temperature and then filtered. The filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in dichloromethane, and the insoluble material was removed by filtration. The solid obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent: ethyl acetate and methanol) to obtain (Ir-61) in a yield of 48%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/acetone-d ₆ )δ: 9.15 (d, 1H), 8.89 (dd, 2H), 8.61 (d, 2H), 8.27 (t, 1H), 8.17 (s, 1H), 8.08 (d, 1H), 7.88 (d, 1H), 7.68 (t, 1H), 2.83 (q, 2H), 2.68 (q , 2H), 1.35 (t, 6H), 1.05 (s, 18H).

< Reference Example I-15>
Synthesis of compound of the present invention (Ir-62)

Step 1 Synthesis of compound (I)

0.679 g of 2-chloro-5-ethylpyrimidine, 1.406 g of 2,6-dimethoxypyridine-3-boronic acid MIDA ester, 10 ml of 2M aqueous solution of tripotassium phosphate, and 60 ml of dioxane were placed in a three-necked flask, and argon gas was introduced. Was bubbled, 0.291 g of tetrakistriphenylphosphine palladium (0) was added, and the mixture was heated and reacted at 60° C. for 24 hours in an argon atmosphere. The reaction solution was cooled to room temperature, filtered through Celite, and the obtained filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: ethyl acetate and hexane) to give compound (I) in a yield of 69. Earned in %. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.65 (s, 2H), 8.18 (d, 1H), 6.43 (d, 1H), 4.06 (s, 3H), 3. 98 (s, 3H), 2.67 (q, 2H), 1.31 (t, 3H).

Step 2 Synthesis of compound (J)

0.294 g of iridium trichloride n hydrate, 0.402 g of compound (I), 0.068 g of potassium carbonate, and 30 ml of DMF were placed in a flask, equipped with an Arene condenser, and microwaved (2450 MHz) while aerating argon gas. , 700 W) for 5 minutes. After the reaction solution was cooled to room temperature, 0.250 g of potassium carbonate was added, and microwave (2450 MHz, 700 W) was irradiated for another 25 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was collected and concentrated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (J) with a yield of 67%.

Step 3 Synthesis of (Ir-62)

0.308 g of compound (I), 0.266 g of picolinic acid, 0.301 g of potassium carbonate, and 40 ml of DMF were placed in a flask, an Aren condenser was attached, and microwaves (2450 MHz, 700 W) were applied while aerating argon gas. Irradiated for minutes. After the reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: ethyl acetate and methanol) to obtain (Ir-62) in a yield of 40%. The data of ¹ H-NMR is shown below. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ )δ: 8.67 (d, 1H), 8.63 (d, 1H), 8.59 (d, 1H), 8.25 (d, 1H), 7.95 (dd, 1H), 7.89 (d, 1H), 7.42 (dd, 1H), 7.26 (d, 1H), 5.37 (s, 1H), 5.18 (s , 1H), 4.05 (s, 3H), 4.02 (s, 3H), 3.81 (s, 3H), 3.77 (s, 3H), 2.63 (q, 2H), 2 .45 (q, 2H), 1.23 (t, 3H), 1.08 (t, 3H).

< Reference Example I-16>
Synthesis of the compound of the present invention (Ir-65)

Step 1 Synthesis of compound (K)

2-chloro-4-methylpyrimidine 0.0799 g, 2,6-dimethoxy-3-(4,4,5,5-tetramethyl-1,3,2-diogizaborolan-2-yl)pyridine 0.151 g, 2M 20 ml of an aqueous potassium carbonate solution, 0.0091 g of SPhos, and 20 ml of toluene were placed in a three-necked flask, argon gas was bubbled through, and 0.0051 g of tris(dibenzylideneacetone)dipalladium(0) was added thereto, and the mixture was heated to 100 under an argon atmosphere. The mixture was heated at 17°C for 17 hours. The reaction solution was cooled to room temperature and then filtered through Celite, and the obtained filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: ethyl acetate and hexane) to give compound (K) in a yield of 85. Earned in %. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ:8.66 (d,1H),8.16 (d,1H),7.01 (d,1H),6.42 (d,1H),4. 04 (s, 3H), 3.98 (s, 3H), 2.57 (s, 3H).

Step 2 Synthesis of compound (L)

0.339 g of iridium trichloride n hydrate, 0.434 g of compound (K), 1.03 g of potassium carbonate, and 40 ml of DMF were placed in a flask, and an Aren condenser was attached to the flask. , 700 W) for 30 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous sodium hydrogen carbonate solution, then the organic layer was collected and concentrated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (L) in a yield of 78%.

Step 3 Synthesis of (Ir-65)

0.401 g of compound (L), 0.358 g of picolinic acid, 0.403 g of potassium carbonate, and 40 ml of DMF were placed in a flask, an Arene condenser was attached, and microwaves (2450 MHz, 700 W) were irradiated for 30 minutes while aerating argon gas. did. The reaction solution was cooled to room temperature, the solvent was concentrated under reduced pressure, and water was added. The precipitated product was collected by filtration, recrystallized using dichloromethane and hexane, and further purified by silica gel column chromatography (eluent: ethyl acetate and methanol) to give (Ir-65) in a yield of 86. Earned in %.
¹ H-NMR (400 MHz/CD ₂ CL ₂ ) δ: 8.53 (d, 1H), 8.21 (d, 1H), 7.92 (t, 1H), 7.85 (d, 1H), 7.38 (dd, 1H), 7.34 (d, 1H), 6.88 (d, 1H), 6.71 (d, 1H), 5.42 (s, 1H), 5.24 (s , 1H), 4.04 (s, 3H), 4.02 (s, 3H), 3.82 (s, 3H), 3.78 (s, 3H), 2.68 (s, 3H), 2 .65 (s, 3H).

< Reference Example I-17>
Synthesis of compound of the present invention (Ir-25)

Step 1 Synthesis of compound (M)

2-Bromo-pyrimidine (8.02 g), 2,6-dimethoxy-3-pyridineboronic acid (9.95 g), 2M aqueous potassium carbonate solution (120 ml) and tetrahydrofuran (100 ml) were placed in a three-necked flask, and argon gas was bubbled through the mixture, followed by tetrakis(triphenylphosphine). ) Palladium (0) 3.86 g was added, and the mixture was heated and reacted at 70 to 77° C. for 45 hours under an argon atmosphere. After cooling the reaction solution to room temperature, the organic layer was collected, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane) to obtain the compound (M) in a yield of 32%. .. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.82 (d, 2H), 8.24 (d, 1H), 7.15 (t, 1H), 6.44 (d, 1H), 4. 06 (s, 3H), 3.99 (s, 3H).

Step 2 Synthesis of compound (N)

1.86 g of iridium trichloride n hydrate, 2.50 g of compound (M), 50 ml of DMF, and 10 ml of pure water were placed in a flask, equipped with a Dimroth condenser, and microwaved (2450 MHz, 500 W) while aerating argon gas. For 45 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. After adding methanol and pure water to this, this was filtered and washed with pure water. The obtained solid was dissolved in dichloromethane and washed with a 10% aqueous potassium carbonate solution, and then the organic layer was collected and evaporated under reduced pressure. This was recrystallized using dichloromethane and hexane to obtain the compound (N) in a yield of 73%.

Step 3 Synthesis of (Ir-25)

0.60 g of compound (N), 4.98 g of compound (M) and 46 ml of diglyme were placed in a three-necked flask, equipped with a Dimroth condenser, and heated and reacted at 180° C. for 48 hours under an argon gas atmosphere. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. 50 ml of diethyl ether was added to this and dispersed, and then filtered through Celite. Further, it was purified by silica gel column chromatography (eluent: dichloromethane and acetone) to obtain 0.172 g of a crude product. 0.105 g of this crude product was taken out, 100 ml of THF and 25 ml of pure water were added thereto, and then UV-visible light (>300 nm) was irradiated for 45 minutes using a high pressure mercury lamp (400 W) in an argon atmosphere. The solvent was distilled off under reduced pressure, ethanol was added, and the solid was collected by filtration. This was recrystallized using dichloromethane and hexane to obtain a facial compound (Ir-25) with a yield of 10.1%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.78 (dd, 3H), 7.59 (dd, 3H), 6.75 (t, 3H), 5.99 (s, 3H), 4. 10 (s, 9H), 3.81 (s, 9H).

< Reference Example I-18>
Synthesis of compound of the present invention (Ir-50)

Step 1 Synthesis of compound (O)

2-Chloro-5-ethylpyrimidine (2.44 g), 2,6-dimethoxy-3-pyridineboronic acid (5.00 g), 2M aqueous potassium carbonate solution (60 ml) and tetrahydrofuran (50 ml) were placed in a three-necked flask, and argon gas was bubbled through the mixture, followed by tetrakis. (Triphenylphosphine)palladium(0) (3.86 g) was added, and the mixture was heated and reacted at 70 to 77°C for 23 hours under an argon atmosphere. The reaction solution was cooled to room temperature, the organic layer was collected, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane and methanol) to give compound (O) in a yield of 99%. Got with. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.66 (s, 2H), 8.19 (d, 1H), 6.43 (d, 1H), 4.06 (s, 3H), 3. 99 (s, 3H), 2.67 (q, 2H), 1.31 (t, 3H).

Step 2 Synthesis of compound (P)

1.86 g of iridium trichloride n hydrate, 2.86 g of compound (M), 60 ml of DMF and 12 ml of pure water were placed in a flask, a Dimroth condenser was attached, and a microwave (2450 MHz, 500 W) was applied while aerating argon gas. Irradiate for 40 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. Pure water was added thereto, and the suspension was filtered and washed with pure water to obtain the compound (P) with a yield of 83%.

Step 3 Synthesis of (Ir-50)

1.42 g of compound (P), 0.38 g of (2,4-pentanedionato)sodium and 75 ml of 2-ethoxyethanol were placed in a three-necked flask, a Dimroth condenser was attached, and a microwave (2450 MHz) was passed while aerating argon gas. , 500 W) for 15 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. Then, 50 ml of pure water was added and suspended, and the solid was collected by filtration. After dissolving in dichloromethane, the solvent was distilled off under reduced pressure through a column packed with activated alumina. This was suspended in methanol and filtered to obtain (Ir-50) in a yield of 58%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.71 (d, 2H), 8.35 (d, 2H), 5.31 (s, 2H), 5.23 (s, 1H), 4. 07 (s, 6H), 3.75 (s, 6H), 2.68 (q, 4H), 1.79 (s, 6H), 1.29 (t, 6H).

< Reference Example I-19>
Synthesis of the compound of the present invention (Ir-51)

0.54 g of compound (N), 0.15 g of (2,4-pentanedionato)sodium and 25 ml of 2-ethoxyethanol were placed in a three-necked flask, a Dimroth condenser was attached, and microwaves (2450 MHz) were passed while aerating argon gas. , 400 W) for 15 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. To this, 10 ml of methanol and 10 ml of pure water were added and suspended, and a solid was collected by filtration. This was recrystallized using dichloromethane and hexane to obtain (Ir-51) in a yield of 62%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.84 (dd, 2H), 8.51 (dd, 2H), 7.01 (t, 2H), 5.32 (s, 2H), 5. 22 (s, 1H), 4.08 (s, 6H), 3.76 (s, 6H), 1.79 (s, 6H).

< Reference Example I-20>
Synthesis of compound (Ir-66) of the present invention

0.38 g of compound (N), 0.10 g of sodium picolinate and 20 ml of 2-ethoxyethanol were placed in a three-necked flask, a Dimroth condenser was attached, and microwaves (2450 MHz, 300 W) were irradiated for 7 minutes while aerating argon gas. did. The reaction solution was cooled to room temperature, and the solvent was evaporated under reduced pressure. To this, 15 ml of pure water was added and suspended, and then the solid was collected by filtration. This was recrystallized three times using dichloromethane and hexane to obtain (Ir-66) with a yield of 74%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.82-8.85 (m, 2H), 8.78 (d, 1H), 8.33 (d, 1H), 7.95 (t, 1H). ), 7.88 (d, 1H), 7.49-7.52 (m, 1H), 7.42 (t, 1H), 7.01 (t, 1H), 6.80 (t, 1H). , 5.44 (s, 1H), 5.25 (s, 1H), 4.13 (s, 3H), 4.08 (s, 3H), 3.84 (s, 3H), 3.79 ( s, 3H).

< Reference Example I-21>
Synthesis of compound of the present invention (Ir-81)

1.52 g of compound (N), 0.62 g of silver trifluoromethanesulfonate, 100 ml of methanol and 150 ml of dichloromethane were placed in a three-necked flask, and reacted under an argon gas atmosphere at room temperature for 36 hours. The reaction solution was filtered through Celite, and the solvent was evaporated under reduced pressure. To this, 0.37 g of 2-phenylpyridine, 9 ml of methanol and 21 ml of ethanol were added, and the mixture was heated and reacted at 85°C to 90°C for 27 hours under an argon atmosphere. After the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure. To this, 100 ml of dichloromethane was added, and the mixture was filtered through Celite, and the filtrate was washed with a 10% aqueous potassium carbonate solution, and then the organic layer was collected and evaporated under reduced pressure. This was purified by silica gel column chromatography (eluent: dichloromethane and methanol) to obtain a meridional (Ir-81) in a yield of 1.6%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.60-8.64 (m, 2H), 8.13 (dd, 1H), 7.95 (d, 1H), 7.92 (d, 1H). ), 7.73 (d, 1H), 7.63-7.69 (m, 2H), 6.98-7.04 (m, 3H), 6.93 (t, 1H), 6.61 ( q, 2H), 5.69 (s, 1H), 5.47 (s, 1H), 4.12 (d, 6H), 3.84 (s, 3H), 3.81 (s, 3H).

< Reference Example I-22>
Synthesis of compound (Ir-72) of the present invention

0.509 g of compound (R), 0.294 g of compound (E), 0.267 g of silver trifluoromethanesulfonate, 20 ml of ethanol, and 10 ml of dichloromethane were placed in a three-necked flask, and heated under reflux for 62 hours under an argon atmosphere. The reaction solution was cooled to room temperature and evaporated under reduced pressure. This was dissolved in dichloromethane and filtered through Celite. The filtrate was washed with a 10% aqueous sodium hydrogen carbonate solution. The solvent was distilled off under reduced pressure. This was purified using silica gel column chromatography (eluent: ethyl acetate and methanol) to obtain a meridional (Ir-72) in a yield of 70%. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CD ₂ Cl ₂ )δ: 9.35 (s, 1H), 8.19 (d, 1H), 8.16 (d, 1H), 8.12 (d, 1H), 7.37-7.42 (m, 2H), 7.24 (d, 1H), 7.10-7.16 (m, 3H), 7.03 (dd, 2H), 6.96 (d, 1H), 6.51-6.63 (m, 4H), 2.75 (s, 3H), 1.30 (s, 9H).

<Example I-23>
Synthesis of the compound of the present invention (Ir-46)

Step 1 Synthesis of compound (S)

0.936 g of 5-bromo-2-tert-butylpyrimidine, 1.22 g of bis(pinacolato)diboron, 1.45 g of potassium acetate, and 20 ml of dehydrated 1,4-dioxane were placed in a three-necked flask, and after aeration with argon gas , [1,1′-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride Dichloromethane adduct 0.0575 g was added, and the mixture was heated and reacted at 100° C. for 24 hours in an argon atmosphere. After cooling the reaction solution to room temperature, 20 mL of a 2 M aqueous solution of tripotassium phosphate, 20 mL of toluene, 0.414 g of 2-chloro-N,N,5-trimethylpyrimidin-4-amine, and tris(dibenzylideneacetone)dipalladium. (0) 0.0554 g and SPhos 0.0796 g were added, and the mixture was heated and reacted at 110° C. for 24 hours in an argon atmosphere. The reaction solution was cooled to room temperature, filtered through Celite, and ethyl acetate was added to the filtrate for extraction. The product obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (eluent: ethyl acetate and dichloromethane) to obtain the compound (S) in a yield of 42%. The data of ¹ H-NMR is shown below.
The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 9.55 (s, 2H), 8.10 (s, 1H), 3.18 (s, 6H), 2.34 (s, 3H), 1. 46 (9H).

Step 2 Synthesis of compound (T)

0.0603 g of iridium trichloride n hydrate, 0.102 g of compound (S), 0.077 g of potassium carbonate, and 15 ml of DMF were placed in a flask, equipped with an Aren condenser, and microwaved at 2450 MHz while aerating argon gas. , 700 W) for 30 minutes. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was recrystallized using dichloromethane and hexane to obtain the compound (T) in a yield of 86%.

Step 3 Synthesis of (Ir-46)

0.107 g of compound (T), 0.0771 g of acetylacetone, 0.0947 g of potassium carbonate, and 15 ml of DMF were placed in a flask, equipped with an arene condenser, and microwaved (2450 MHz, 700 W) for 30 minutes while aerating argon gas. Irradiated. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane, washed with water, and the solution was evaporated under reduced pressure. Further purification was performed using silica gel column chromatography (eluent: ethyl acetate and dichloromethane) to obtain (Ir-46) in a yield of 30%. The data of ¹ H-NMR is shown below. The data of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz/CDCl ₃ ) δ: 8.43 (s, 2H), 7.86 (s, 2H), 5.23 (s, 1H), 3.25 (s, 12H), 2. 35 (s, 6H), 1.88 (s, 6H), 1.09 (s, 18H).

Next, the emission characteristics of the iridium complex according to the present invention in a solution will be described.

<Example II-1>
Luminescence characteristics of the compound of the present invention (Ir-4) in THF The compound of the present invention (Ir-4) was dissolved in THF and argon gas was passed through, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure an emission spectrum (excitation wavelength: 350 nm) at room temperature, it showed blue-green emission (emission maximum wavelength: 507 nm). The emission quantum yield was 0.62.

< Reference Example II-2>
Luminescence characteristics of the compound of the present invention (Ir-25) in chloroform After dissolving the compound of the present invention (Ir-25) in chloroform and ventilating an argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, it showed blue-green emission (emission maximum wavelength: 492 nm). The emission quantum yield was 0.78.

<Example II-3>
Luminescent properties of the compound of the present invention (Ir-38) in THF The compound of the present invention (Ir-38) was dissolved in THF, and after ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, which showed blue-green emission (emission maximum wavelength: 496 nm). The emission quantum yield was 0.83.

<Example II-4>
Luminescence characteristics of the compound of the present invention (Ir-42) in THF After dissolving the compound of the present invention (Ir-42) in THF and ventilating an argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum at room temperature (excitation wavelength: 350 nm), it showed blue-green emission (emission maximum wavelength: 489 nm). The emission quantum yield was 0.62.

<Example II-5>
Luminescence characteristics of the compound of the present invention (Ir-47) in THF The compound of the present invention (Ir-47) was dissolved in THF, and argon gas was passed through the device, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 475,504 nm) was observed. The emission quantum yield was 0.55.

<Example II-6>
Luminescent Properties of Compound of the Present Invention (Ir-48) in THF After dissolving the compound of the present invention (Ir-48) in THF and ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 476,504 nm) was observed. The emission quantum yield was 0.55.

< Reference Example II-7>
Luminescence characteristics of the compound of the present invention (Ir-50) in chloroform After dissolving the compound of the present invention (Ir-50) in chloroform and ventilating an argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure an emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 481,504 nm) was shown. The emission quantum yield was 0.85.

< Reference Example II-8>
Luminescent Properties of Compound of the Present Invention (Ir-51) in Chloroform The compound of the present invention (Ir-51) was dissolved in chloroform, and argon gas was passed through the device, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 478,500 nm) was observed. The emission quantum yield was 0.80.

<Example II-9>
Luminescence characteristics of the compound of the present invention (Ir-52) in THF The compound of the present invention (Ir-52) was dissolved in THF, and after ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum at room temperature (excitation wavelength: 350 nm), which showed blue-green emission (emission maximum wavelength: 480 nm). The emission quantum yield was 0.87.

<Example II-10>
Luminescence characteristics of the compound of the present invention (Ir-53) in THF The compound of the present invention (Ir-53) was dissolved in THF, and argon gas was passed through the device, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure an emission spectrum (excitation wavelength: 350 nm) at room temperature, and as a result, blue emission (maximum emission wavelength: 471, 497 nm) was shown as shown in FIG. The emission quantum yield was 0.72.

<Example II-11>
Luminescence characteristics of the compound of the present invention (Ir-56) in THF The compound of the present invention (Ir-56) was dissolved in THF and an argon gas was passed through, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure the emission spectrum at room temperature (excitation wavelength: 350 nm), and blue emission (maximum emission wavelength: 462, 494 nm) was shown. The emission quantum yield was 0.53.

<Example II-12>
Luminescence characteristics of the compound of the present invention (Ir-59) in THF The compound of the present invention (Ir-59) was dissolved in THF and an argon gas was passed through the device, and then an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure an emission spectrum (excitation wavelength: 350 nm) at room temperature, and as a result, blue emission (maximum emission wavelength: 462, 491 nm) was shown as shown in FIG. The emission quantum yield was 0.53.

<Example II-13>
Luminescent properties of the compound of the present invention (Ir-60) in THF The compound of the present invention (Ir-60) was dissolved in THF, and after ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 470, 500 nm) was observed. The emission quantum yield was 0.03.

<Example II-14>
Luminescent Properties of Compound of the Present Invention (Ir-61) in THF After dissolving the compound of the present invention (Ir-61) in THF and ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 457,489 nm) was shown. The emission quantum yield was 0.03.

< Reference Example II-15>
Luminescent properties of the compound of the present invention (Ir-62) in THF The compound of the present invention (Ir-62) was dissolved in THF, and after ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure an emission spectrum (excitation wavelength: 350 nm) at room temperature, and it showed blue emission (emission maximum wavelength: 473, 498 nm). The emission quantum yield was 0.88.

< Reference Example II-16>
Luminescent Properties of Compound of the Present Invention (Ir-65) in THF After dissolving the compound of the present invention (Ir-65) in THF and ventilating with argon gas, an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 462, 489 nm) was observed. The emission quantum yield was 0.81.

< Reference Example II-17>
Luminescent Properties of Compound of the Present Invention (Ir-66) in Chloroform The compound of the present invention (Ir-66) was dissolved in chloroform, and an argon gas was bubbled through the device, followed by an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics K.K. Was used to measure the emission spectrum (excitation wavelength: 350 nm) at room temperature, and blue emission (maximum emission wavelength: 463,489 nm) was observed. The emission quantum yield was 0.83.

<Comparative Example II-1>
Luminescent Properties of Comparative Compound (A) in THF The comparative compound (A) described in International Publication No. 2011/024737 (Patent Document 5) is dissolved in THF, and an argon gas is passed through the product, which is manufactured by Hamamatsu Photonics K.K. When an emission spectrum (excitation wavelength: 350 nm) at room temperature was measured by using the absolute PL quantum yield measuring apparatus (C9920), a green emission (maximum emission wavelength: 532 nm) was shown. The emission quantum yield was 0.67.

When the maximum emission wavelengths of the compounds (Ir-42) and (Ir-48) of the present invention and the comparative compound (A) are compared, as shown in Table 8, the emission of the compound of the present invention is blue-shifted by 43 to 56 nm. I understand. Therefore, it was revealed that the compound of the present invention is superior as a blue light emitting material.

Next, the light emission characteristics of the thin film of the iridium complex according to the present invention will be described.

<Example III-1>
Luminescent Properties of Thin Film of Compound (Ir-47) of the Present Invention Iridium complex (Ir-47) of the present invention and 1,3-bis(N-carbazolyl)benzene (hereinafter, referred to as mCP) were used at a vacuum degree of 1×10. ^-4 Pa, co-deposited (30 nm) at 5:95 (mass concentration ratio) on a quartz substrate, and using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK, emission spectrum at room temperature. When the (excitation wavelength: 340 nm) was measured, blue light emission (emission maximum wavelength: 472, 502 nm) was shown. The emission quantum yield was 0.89.

< Reference Example III-2>
Light-Emitting Properties in Thin Film of Compound (Ir-51) of the Present Invention The iridium complex (Ir-51) of the present invention and mCP were mixed at a vacuum degree of 1×10 ⁻⁴ Pa on a quartz substrate at a ratio of 5:95 (mass concentration ratio). ) Was co-deposited (30 nm), and the emission spectrum (excitation wavelength: 340 nm) at room temperature was measured using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics Co., Ltd. Wavelength: 474,499 nm) was shown. The emission quantum yield was 0.89.

<Example III-3>
Light-Emitting Properties in Thin Film of Compound (Ir-52) of the Present Invention The iridium complex (Ir-52) of the present invention and mCP were applied at a vacuum degree of 1×10 ⁻⁴ Pa on a quartz substrate at a ratio of 5:95 (mass concentration ratio). ) Was co-deposited (30 nm), and the emission spectrum (excitation wavelength: 340 nm) at room temperature was measured using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics Co., Ltd. Wavelength: 474, 501 nm). The emission quantum yield was 0.90.

<Example III-4>
Light-Emitting Properties in Thin Film of Compound (Ir-53) of the Present Invention The iridium complex (Ir-53) of the present invention and mCP were mixed at a vacuum degree of 1×10 ⁻⁴ Pa on a quartz substrate at a ratio of 5:95 (mass concentration ratio). ), and the emission spectrum (excitation wavelength: 340 nm) at room temperature was measured using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK, as shown in FIG. Blue emission (maximum emission wavelength: 468, 496 nm). The emission quantum yield was 0.88.

<Example III-5>
Light-Emitting Properties in Thin Film of Compound of the Present Invention (Ir-59) The iridium complex (Ir-59) of the present invention and mCP were mixed on a quartz substrate at 5:95 (mass concentration ratio) at a vacuum degree of 1×10 ⁻⁴ Pa. ), co-evaporation (30 nm) was performed, and the emission spectrum (excitation wavelength: 340 nm) at room temperature was measured using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK, as shown in FIG. Blue emission (maximum emission wavelength: 460, 489 nm) was exhibited. The emission quantum yield was 0.62.

<Example III-6>
Luminescent properties of the compound (Ir-59) of the present invention in a thin film The iridium complex (Ir-59) of the present invention and 2,7-bis(diphenylphosphoryl)-9-phenyl-9H-carbazole were used at a vacuum degree of 1×10. ^-4 Pa, co-deposited (30 nm) at 5:95 (mass concentration ratio) on a quartz substrate, and using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics KK, emission spectrum at room temperature. When the (excitation wavelength: 340 nm) was measured, blue light emission (emission maximum wavelength: 462, 489 nm) was shown. The emission quantum yield was 0.74.

< Reference Example III-7>
Light-Emitting Properties in Thin Film of Compound (Ir-66) of the Present Invention The iridium complex (Ir-66) of the present invention and mCP were applied at a vacuum degree of 1×10 ⁻⁴ Pa on a quartz substrate at a ratio of 5:95 (mass concentration ratio). ) Was co-deposited (30 nm), and the emission spectrum (excitation wavelength: 340 nm) at room temperature was measured using an absolute PL quantum yield measuring device (C9920) manufactured by Hamamatsu Photonics Co., Ltd. Wavelength: 465, 492 nm). The emission quantum yield was 0.72.

Next, the characteristics of the organic electroluminescence device produced by using the iridium complex represented by the general formula (1) according to the present invention will be described.

The structural formulas of the compounds (E-1) to (E-9) used in this example are shown below.

<Example IV-1>
Characteristic Evaluation of Organic Electroluminescent Device Produced Using Compound of the Present Invention (Ir-47) As an anode, an indium tin oxide (ITO) film having a film thickness of 100 nm was patterned into a comb shape having a line width of 2 mm to form a non-alkali film. A glass substrate (manufactured by Atsugi Micro Co., Ltd.) was used as a transparent conductive support substrate. This was ultrasonically cleaned successively with ultrapure water, acetone, and isopropyl alcohol (IPA), then washed by boiling with IPA and then dried. Then, what was washed with UV/ozone was used as a transparent conductive support substrate.

On the transparent conductive support substrate, the following organic layers (hole injection layer, hole transport layer, host material layer, light emitting layer, hole blocking layer, and electron transport layer) were placed in a vacuum chamber of 1×10 ⁻⁴ Pa. The film was sequentially formed by vacuum evaporation by resistance heating in the chamber, and then the mask was replaced to sequentially form electrode layers (electron injection layer and metal electrode layer) having a line width of 2 mm to produce an organic electroluminescence device. Next, a work of sealing the device in a glove box under a nitrogen atmosphere so as not to be exposed to the atmosphere was performed. UV curable epoxy resin Denatite R (manufactured by Nagase Chemitech) is applied to the periphery of a sealing glass (manufactured by Senyo Shoji Co., Ltd.) in which a 1.5 mm cutout is attached to the center of a 3 mm thick glass plate and vapor deposition After covering the finished element and pressure bonding, the element portion was covered with an aluminum plate for masking, irradiation with a UV irradiation device with a shutter for 1 minute, and then a shielding cycle of 1 minute was repeated 5 times for sealing.

Hole injection layer (10 nm): Compound (E-1)
First hole transport layer (40 nm): Compound (E-2)
Second hole transport layer (10 nm): Compound (E-3)
Light-emitting layer (20 nm): Inventive compound (Ir-47) (mass concentration 15%) and compound (E-3) (mass concentration 85%) are co-deposited Hole blocking layer (10 nm): Compound (E-4) )
Electron transport layer (30 nm): Compound (E-5)
Electron injection layer (1 nm): Compound (E-6)
Metal electrode layer (100 nm): Al

The obtained organic electroluminescent element was set in a sample holder of an integrating sphere unit A10094 for measuring EL external quantum yield manufactured by Hamamatsu Photonics KK, and a constant DC voltage was applied using a source meter 2400 manufactured by Keithley to emit light. , Its luminance, emission wavelength and CIE chromaticity coordinates were measured using a multi-channel spectroscope PMA-12 manufactured by Hamamatsu Photonics. As a result, blue light emission with CIE chromaticity (x, y)=(0.21, 0.44), emission peak wavelength of 475, 503 nm was obtained, maximum luminance was 34500 cd/m ² , and external quantum efficiency was 4 Emission characteristics of 0.8% (at 1000 cd/cm ² ) were obtained.

<Example IV-2>
Characteristic Evaluation of Organic Electroluminescent Device Produced Using Inventive Compound (Ir-52) Using Inventive Compound (Ir-52) Instead of Inventive Compound (Ir-47) Used in Example IV-1 An organic electroluminescence device was prepared in the same manner except that the mass concentrations of the compound (Ir-52) of the present invention and the compound (E-3) were changed to 5% and 95%, respectively, and the characteristics were evaluated. As a result, blue light emission with CIE chromaticity (x, y)=(0.18, 0.42), emission peak wavelengths of 477, 503 nm was obtained, the maximum luminance was 30300 cd/m ² , and the external quantum efficiency was 4 A luminescence property of 0.9% (at 1000 cd/cm ² ) was obtained.

<Example IV-3>
Characteristic Evaluation of Organic Electroluminescent Device Produced Using Compound of the Present Invention (Ir-53) The compound of the present invention (Ir-53) was used instead of the compound of the present invention (Ir-47) used in Example IV-1. An organic electroluminescence device was prepared in the same manner except that the mass concentrations of the compound (Ir-53) of the present invention and the compound (E-3) were changed to 5% and 95%, respectively, and the characteristics were evaluated. As a result, blue emission with CIE chromaticity (x, y)=(0.18, 0.39), emission peak wavelength of 469, 497 nm was obtained, maximum luminance was 21000 cd/m ² , and external quantum efficiency was 5 A light emission characteristic of 0.4% (at 1000 cd/cm ² ) was obtained.

<Example IV-4>
Characteristic Evaluation of Organic Electroluminescent Device Produced Using Compound of the Present Invention (Ir-59) The light emitting device of Example IV-1 was changed to the following constitution, and an organic electroluminescent device was similarly prepared, and characteristic evaluation was performed. I went.

Hole injection layer (10 nm): Compound (E-1)
First hole transport layer (30 nm): Compound (E-7)
Second hole transport layer (10 nm): Compound (E-3)
Light-emitting layer (30 nm): Compound (Ir-59) of the present invention (mass concentration 15%) and compound (E-8) (mass concentration 85%) are co-deposited Electron transport layer (30 nm): Compound (E-9)
Electron injection layer (1 nm): Compound (E-6)
Metal electrode layer (100 nm): Al

As a result, CIE chromaticity was (x, y)=(0.17, 0.31), blue light emission with an emission peak wavelength of 462, 490 nm was obtained as shown in FIG. 5, and the maximum luminance was 4720 cd/m ^2. The external quantum efficiency was 10.1% (at 1000 cd/m ² ) and the emission characteristics were obtained.

As described above, the iridium complex represented by the general formula (1) according to the present invention is excellent in thermal stability and sublimation property and exhibits a high emission quantum yield in the visible light region (particularly in the blue region). When it is a novel compound and is used for an organic light emitting device, an organic light emitting device having good light emitting characteristics can be produced. Further, an organic light emitting device using the compound exhibits high-luminance emission in the visible light region (particularly in the blue region), and is therefore suitable for fields such as display devices, displays, backlights, and illumination light sources.

Claims (12)

An iridium complex represented by the following general formula (1).

(In the general formula (1), N represents a nitrogen atom, Ir represents iridium, X represents C(R ⁶ ), or a nitrogen atom. R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group. , An aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, R ^{4 to} R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group. Provided that at least one of R ⁴ and R ⁵ is an alkyl group, and the alkyl group, alkoxy group, or aryloxy group of R ^{4 to} R ⁶ is not substituted with fluorine. When (R ⁶ ), R ⁴ and R ⁵ are alkyl groups, or when R ⁴ is a hydrogen atom and R ⁵ is an alkyl group, and when X is a nitrogen atom, R ⁴ is a hydrogen atom and R ⁵ Is an alkyl group. R ¹ and R ² , and R ² and R ³ may be bonded to each other to form a ring structure, m= 2 to 3 , n= 0 to 1 and m+n. =3. L represents a monoanionic bidentate ligand.) The iridium complex according to claim 1, wherein R ^{1 to} R ³ are hydrogen atoms or alkyl groups. The iridium complex according to claim 1, wherein R ⁴ and R ⁵ are alkyl groups. Iridium complex according to any one of claims 1-3, characterized in that X is C (R ^6). Iridium complex according to any one of claims 1-3, characterized in that X is a nitrogen atom. L iridium complex according to any one of claims 1-5, characterized in that the nitrogen-containing heterocyclic ligands or diketone ligand. L is Formula (2) to (10) iridium complex according to any one of claims 1-6, characterized in that at least one selected from among.

(In formulas (2) to (10), R ^{7 to} R ⁶⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom. In addition, adjacent substituents may combine with each other to form a ring structure, X ² represents C(R ⁷⁰ ), or a nitrogen atom, and R ^{65 to} R ⁶⁷ each independently represent a hydrogen atom, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, and each of R ^{68 to} R ⁷⁰ independently represents a hydrogen atom, an alkyl group, an alkoxy group, or aryl. Represents an oxy group, provided that at least one of R ⁶⁸ and R ⁶⁹ is an alkyl group or an alkoxy group, R ⁶⁵ and R ⁶⁶ , and R ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring structure. Good.) iridium complex according to any one of claims 1-5, characterized in that m is 3. The iridium complex according to any one of claims 1 to 8 , wherein m is 2 and n is 1. Luminescent material characterized by comprising iridium complex according to any one of claims 1-9. An organic light emitting device comprising the light emitting material according to claim 10 . A compound represented by the general formula (11).

(In the general formula (11), N represents a nitrogen atom, Ir represents iridium, X represents C(R ⁶ ) or a nitrogen atom, Y represents a halogen atom, and R ^{1 to} R ³ are each independently. Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an aryloxy group, or a halogen atom, and R ^{4 to} R ⁶ are each independently a hydrogen atom, an alkyl group, or an alkoxy group. Represents a group or an aryloxy group, provided that at least one of R ⁴ and R ⁵ is an alkyl group, and the alkyl group, alkoxy group, or aryloxy group of R ^{4 to} R ⁶ is substituted with fluorine. When X is C(R ⁶ ), R ⁴ and R ⁵ are alkyl groups, or when R ⁴ is a hydrogen atom and R ⁵ is an alkyl group and X is a nitrogen atom, R is ⁴ is a hydrogen atom and R ⁵ is an alkyl group.R ¹ and R ² , and R ² and R ³ may combine with each other to form a ring structure.)

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