JP2009057367A - Metal complex compound, material for organic electroluminescent element and organic electroluminescent element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element in which blue luminescence having high color purity is obtained by luminescence having a short wavelength and white luminescence can also be emitted in combination with another luminescent compound, a metal complex compound realizing the element and a material for the organic electroluminescent element. <P>SOLUTION: The metal complex compound has a specific structure having a bidentate chelate ligand and a tridentate chelate ligand each containing an electron-attracting group. The organic electroluminescent element is constituted so that an organic thin film layer which consists of one or more layers having at least luminescent layer is put between a pair of electrodes. In the electroluminescent element, at least one layer of the organic thin film layer contains the metal complex compound and emits light by applying voltage between the electrodes. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel metal complex compound and an organic electroluminescence device using the same, and in particular, blue light emission with high color purity can be obtained with short-wavelength light emission, and white light emission is also possible in combination with other light-emitting compounds. The present invention relates to an organic electroluminescence device, a metal complex compound that realizes the organic electroluminescence device, and a material for an organic electroluminescence device.

In recent years, the use of an organic electroluminescence (EL) element as a display device for a color display replacing a liquid crystal has been actively studied. However, the light emitting device performance is still insufficient to realize a large screen. As a means for improving the performance of this organic EL device, a green light-emitting device using an orthometalated iridium complex (fac-tris (2-phenylpyridine) iridium) as a phosphorescent light-emitting material has been proposed (Non-patent Document 1). Non-patent document 2).
Organic EL devices using phosphorescence emission, currently limited to green emission and red emission, so the range of application as a color display is narrow. Therefore, development of devices with improved emission characteristics for other colors is desired. It was. In particular, no blue light emitting element has been reported that has an external quantum yield exceeding 5%. If the blue light emitting element can be improved, full color and whitening can be achieved. Advance.

  Currently, active development of metal complex compounds containing Ir as phosphorescent complexes is known, and the following compound A is known for green light emitting devices. On the other hand, the following compound B is known as a blue light emitting device, but it is not practical in terms of device life and efficiency. Therefore, there is a need to develop other complexes for blue light-emitting elements, but at present, no complex other than Compound B has been found.

  The above compounds A and B are complexes using a bidentate chelate ligand, but few complexes using a similar tridentate chelate ligand are known, and the following compound C is known. (See Non-Patent Document 3).

However, the emission wavelength obtained from Compound C is 600 nm red region light emission and not blue region light emission. If a complex using such a tridentate chelate ligand can realize a blue light emitting complex, there is a possibility of new technological development.
Patent Documents 1 and 2 disclose metal complex compounds having a tridentate chelate ligand, but light having a shorter wavelength can be obtained by adding an electron-withdrawing group to a specific site of the metal complex compound. There is no disclosure of a technique for emitting light.

D.F.O'Brien and M.A.Baldo et al "Improved energy transferin electrophosphorescent devices" Applied Physics letters Vol.74 No.3, pp442-444, January 18, 1999 M.A.Baldo et al "Very high-efficiencygreen organic light-emitting devices based on electrophosphorescence" Applied Physics letters Vol. 75 No.1, pp4-6, July 5, 1999 J-P. Collin et.al., J.Am.Chem.Soc., 121,5009 (1999) International Publication No. 2006/051806 Pamphlet JP 2006-160724 A

  The present invention has been made to solve the above-mentioned problems, and an organic EL device capable of emitting blue light with high color purity by light emission at a short wavelength and capable of white light emission in combination with other light-emitting compounds, and the same It aims at providing the metal complex compound which implement | achieves, and the material for organic EL elements.

When the present inventors use a metal complex compound having a structure having a bidentate chelate ligand and a tridentate chelate ligand represented by the following general formula (I) and having an electron withdrawing group, The present inventors have completed the present invention by clarifying a new structural factor of bluening that blue light emission with high color purity can be obtained by light emission at a wavelength.
That is, this invention provides the metal complex compound which has a structure represented by the following general formula (I) which has a bidentate chelate ligand and a tridentate chelate ligand.

(In the formula, ring A is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
Ring B is an optionally substituted heterocyclic group having 2 to 20 carbon atoms, N is a nitrogen atom, Y is a carbon atom or a nitrogen atom,
L and Z are each independently an organic group containing any atom of Groups 14-16 of the Periodic Table;
X is a monovalent ligand containing any atom of Groups 14-17 of the Periodic Table;
R is a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkylamino group having 1 to 12 carbon atoms, C6-C20 arylamino group which may have a substituent, C1-C12 alkoxy group which may have a substituent, C1-C12 halogen which may have a substituent An alkoxy group, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, and a substituent. It has a C2-C20 heterocyclic group, a C1-C12 halogenated alkyl group which may have a substituent, a C2-C12 alkenyl group which may have a substituent, and a substituent. An alkynyl group having 2 to 12 carbon atoms, or 3 to 20 carbon atoms which may have a substituent A cycloalkyl group. n is an integer of 0 to 4, and when n is 2 or more, each R may be the same or different, and adjacent ones may be bonded to each other to form a cyclic structure.
However, the tridentate chelate ligand and / or the bidentate chelate ligand contains an electron-withdrawing group. )
Further, the present invention provides an organic EL device material comprising the metal complex compound, and an organic EL device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes. At least one layer of the organic thin film layer contains the metal complex compound, and provides an organic EL device that emits light by applying a voltage between both electrodes.
Furthermore, an organic EL device that emits white light with high color purity is provided by simultaneously using the metal complex compound and the red light emitting material as the light emitting dopant of the light emitting layer.

  The present invention provides an organic EL device that has high luminous efficiency, has a short emission wavelength, emits blue light with high color purity, and can emit white light in combination with other light-emitting compounds, and a metal complex compound that realizes the organic EL device. provide.

The metal complex compound of the present invention has a structure represented by the following general formula (I) having a bidentate chelate ligand and a tridentate chelate ligand.

In general formula (I), ring A is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. , Ring B is an optionally substituted heterocyclic group having 2 to 20 carbon atoms, N is a nitrogen atom, and Y is a carbon atom or a nitrogen atom.
Examples of the aromatic hydrocarbon group of ring A include residues such as benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, terphenyl, and fluoranthene, and an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable. More preferred are benzene residues.
Examples of the heterocyclic group of ring A and ring B include, for example, imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrarodine, imidazolidine, piperidine , Pyrazole, thiazole, oxazole, benzofuran, and the like. A heterocyclic group having 2 to 5 carbon atoms is preferable, and residues of pyridine, pyrazole, thiazole, oxazole, and benzofuran are more preferable. As the heterocyclic group of ring B, a pyridine residue is particularly preferable.
In addition, the substituents that each of these groups may have include a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted carbon number of 1 to 12 (preferably An alkyl group having 1 to 5 carbon atoms, a fluorine-substituted alkyl group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms), a substituted or unsubstituted 2 to 12 carbon atoms (preferably 2 to 8 carbon atoms). An alkenyl group, a substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms (preferably 5 to 8 carbon atoms), a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms), A substituted or unsubstituted heterocyclic group having 2 to 5 carbon atoms, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, Carboxyl group, and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the amino group include an alkylamino group in which the hydrogen atom of the amino group is substituted with an alkyl group having 1 to 12 carbon atoms; and an arylamino group in which the hydrogen atom of the amino group is substituted with an aryl group having 6 to 20 carbon atoms. It is done.
Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n- A heptyl group, n-octyl group, etc. are mentioned.
Examples of the alkenyl group include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.
Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, and a t-butoxy group.
Examples of the heterocyclic group include residues such as imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrarodine, imidazolidine, and piperidine. .
As an arylalkyl group, the said aryl group is substituted by the said alkyl group, for example, a benzyl group etc. are mentioned.
Examples of the aryloxy group include those in which the aryl group moiety is the above aryl group.
Examples of the alkoxycarbonyl group include those in which the alkoxy group moiety is the above alkoxy group.

In the general formula (I), L and Z are each independently an organic group containing any atom of Groups 14 to 16 in the periodic table.
As atoms of Groups 14-16 of the periodic table contained in L and Z, C (carbon), N (nitrogen), O (oxygen), Si (silicon), P (phosphorus), S (sulfur), Examples include Ge (germanium), As (arsenic), Se (selenium) atoms, and carbon, nitrogen, and oxygen atoms are preferable.
Moreover, as an organic group which L and Z show, respectively, the C1-C12 alkyl group which may have a substituent, and the C1-C12 alkylamino group which may have a substituent are each independently. , An arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent It may have a halogenated alkoxy group, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, or a substituent. A C2-C20 heterocyclic group, a C1-C12 halogenated alkyl group that may have a substituent, a C2-C12 alkenyl group that may have a substituent, and a substituent; C2-C12 alkynyl group which may have, or C3-C2 which may have a substituent Preferably a cycloalkyl group.

Examples of the alkyl group include a 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- A heptyl group, n-octyl group, etc. are mentioned.
Examples of the aromatic hydrocarbon group include residues such as benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, terphenyl, and fluoranthene.
Examples of the heterocyclic group include residues such as imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrarodine, imidazolidine, and piperidine. Can be mentioned.
Examples of the alkylamino group include those in which a hydrogen atom of an amino group is substituted with the alkyl group.
Examples of the arylamino group include those in which a hydrogen atom of the amino group is substituted with the aromatic hydrocarbon group.
The alkoxy group is represented as -OY ', and examples of Y' include the same as those mentioned for the alkyl group.
Examples of the halogenated alkoxy group include those in which a hydrogen atom of the alkoxy group is substituted with the halogen atom.
The aryloxy group is represented as —OY ″, and examples of Y ″ include the same as those mentioned for the aromatic hydrocarbon group.
Examples of the halogenated alkyl group include those in which a hydrogen atom of the alkyl group is substituted with the halogen atom.
Examples of the alkenyl group include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.
Examples of the alkynyl group include an ethynyl group and a methylethynyl group.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
Moreover, as a substituent which these each group may have, the substituent similar to what was illustrated as a substituent which the ring A and B may have is mentioned.

が挙げられ、シアノ基、塩素原子、臭素原子、ヨウ素原子、アルコキシ基、水素原子、Ｓｉ（Ｒ’）₃又は置換フェニル基が好ましく挙げられる。 In the general formula (I), X is a monovalent ligand containing any atom of Groups 14 to 17 of the periodic table.
The atoms in Groups 14 to 17 of the periodic table contained in X include C (carbon), N (nitrogen), O (oxygen), F (fluorine), Si (silicon), P (phosphorus), S ( Sulfur), Cl (chlorine), Ge (germanium), As (arsenic), Se (selenium), Br (bromine), I (iodine) atoms and the like, and carbon, nitrogen, chlorine, bromine and iodine atoms are preferred. .
In addition, as a ligand represented by X, a cyano group, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, a hydrogen atom, Si (R ′) ₃ (R ′ represents the same group as the following R), substitution, Or an unsubstituted phenyl group and the following group

A cyano group, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, a hydrogen atom, Si (R ′) ₃ or a substituted phenyl group is preferably exemplified.

In general formula (I), R is a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or an optionally substituted carbon group having 1 carbon atom. May have an alkylamino group of -12, an arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and a substituent. C1-C12 halogenated alkoxy group, C6-C20 aryloxy group which may have a substituent, C6-C20 aromatic hydrocarbon group which may have a substituent, Substitution A C2-C20 heterocyclic group which may have a group, a C1-C12 halogenated alkyl group which may have a substituent, and a C2-C12 which may have a substituent An alkenyl group, an alkynyl group having 2 to 12 carbon atoms that may have a substituent, or a substituent Also cycloalkyl group optionally 3 to 20 carbon atoms, and specific examples of each of these groups include the same examples and L and Z.
Among these, a hydrogen atom, an isopropyl group, a t-butyl group, and a methyl group are preferable.
Further, n is an integer of 0 to 4, and when n is 2 or more, each R may be the same or different, and adjacent ones may be bonded to each other to form a cyclic structure. n is preferably 0 or 1.
Examples of the cyclic structure include cycloalkanes (eg, cyclopropane, cyclobutane, cyclopropane, cyclohexane, cycloheptane, etc.), aromatic hydrocarbon rings (eg, benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, terphenyl). , Fluoranthene, etc.) and heterocyclic rings (for example, imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, diphenylanthracene, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrarodine, imidazolidine, piperidine, etc. ).
Moreover, as a substituent which these each group may have, the substituent similar to what was illustrated as a substituent which the ring A and B may have is mentioned.

In the metal complex compound of the present invention, in the general formula (I), the tridentate chelate ligand and / or the bidentate chelate ligand contains an electron-withdrawing group. Moreover, it is preferable that both the tridentate chelate ligand and the bidentate chelate ligand contain an electron-withdrawing group because light emission with a shorter wavelength can be obtained or a higher quantum yield can be obtained.
Examples of the electron withdrawing group include a halogen atom (fluorine, chlorine, bromine, iodine atom, etc.), a cyano group, a nitro group, a halogen atom-containing alkyl group or an ester group, an aldehyde group, and the like. An alkyl group is preferable, and a fluorine atom and a trifluoromethyl group are more preferable.
In this way, the metal complex compound of the present invention stabilizes the HOMO of the metal complex compound by introducing the electron-withdrawing group and acts to widen the energy difference between HOMO and LUMO. Is obtained. This effect is particularly strong when a fluorine atom is used as the electron-withdrawing group. Moreover, since the metal complex compound which introduce | transduced the fluorine atom is excellent in sublimation property, when manufacturing an organic EL element by vapor deposition, it is efficient.
In the metal complex compound of the present invention, since the tridentate chelate ligand has a pyridine ring as an essential structure, the stability of the compound is improved and the quantum yield is also improved.

（式中、環Ｂ、Ｙ、Ｒ及びｎは、前記と同じ。） In the general formula (I), the tridentate chelate ligand is preferably represented by the following general formula (1) or (2), and is a compound represented by any one of (3) to (16). And preferred.

(In the formula, rings B, Y, R and n are the same as described above.)

(Wherein R ^{1 to} R ²³ are the same as R, respectively, and adjacent ones of R ^{1 to} R ²³ may be bonded to each other to form a cyclic structure. Specific examples are also R). The same thing is mentioned.)
Further, examples of the tridentate chelate ligand include the following.

  In the general formula (I), the bidentate chelate ligand formed by LZ is preferably a compound represented by any one of the following general formulas (17) to (22).

（式中、Ｒ²⁴〜Ｒ⁴⁵は、それぞれ前記Ｒと同じであり、またＲ²⁴〜Ｒ⁴⁵のうち隣接するもの同士で互いに結合して環状構造を形成していてもよい。具体例もＲと同様のものが挙げられる。）
さらに、前記２座キレート配位子として、下記のような例が挙げられる。

(Wherein R ^{24 to} R ⁴⁵ are the same as R, respectively, and adjacent ones of R ^{24 to} R ⁴⁵ may be bonded to each other to form a cyclic structure. Specific examples are also R). The same thing is mentioned.)
Further, examples of the bidentate chelate ligand include the following.

The metal complex compound of the present invention is preferably represented by any of the following general formulas (I-1) to (I-12) and (I-13) to (I-24).

(In the formulas (I-1) to (I-12), R ^{46 to} R ⁵⁸ are the same as R. l and l ′ are integers of 0 to 2, and m and m ′ are 0 to 0. N, n ′, n ″ and n ′ ″ are integers from 0 to 4. l, l ′, m, m ′, n, n ′, n ″ or n ″. When 'is 2 or more, two or more of R ^{46 to} R ⁵⁸ may be the same or different, and adjacent ones may be bonded to each other to form a cyclic structure. Specific examples include those similar to R. However, in R ^{46 to} R ⁵⁸ , any one or more of them must be an electron-withdrawing group.
In formulas (I-13) to (I-24), R ⁴⁶ and R ^{48 to} R ⁵⁹ are the same as R. l, l ′ and l ″ are integers of 0 to 2, m is an integer of 0 to 3, and n, n ′, n ″ and n ″ ′ are integers of 0 to 4. When l, l ′, l ″, m, n, n ′, n ″, or n ′ ″ is 2 or more, two or more of R ⁴⁶ and R ^{48 to} R ⁵⁹ may be the same. They may be different, or adjacent ones may be bonded to each other to form a cyclic structure. Specific examples include those similar to R. However, in R ^{48 to} R ⁵⁹ , any one or more needs to be an electron withdrawing group. )
Among these, it is preferable that n is 0 or 1, respectively. In particular, in the metal complex compounds (I-5), (I-9), (I-13), (I-17), and (I-21), when n is 1, R ⁴⁶ and R ⁴⁶ are A C1-C12 alkyl group is preferable, a C1-C5 alkyl group is more preferable, and an isopropyl group and t-butyl group are further more preferable.

Moreover, as a specific example of the metal complex compound of this invention, what consists of a combination of the partial structure as shown in following Table 1 is preferable. It is not limited to these exemplary compounds.

The organic EL device material of the present invention contains the metal complex compound of the present invention.
The organic EL device of the present invention is an organic EL device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes comprising an anode and a cathode. However, it contains the metal complex compound of the present invention and emits light when a voltage is applied between both electrodes.
In the organic EL device of the present invention, the light emitting layer preferably contains the metal complex compound of the present invention, and preferably contains 1 to 30% by mass of the metal complex compound of the present invention based on the total mass of the light emitting layer.
In addition, the light emitting layer is usually thinned by vacuum deposition or coating. However, since the manufacturing process can be simplified by coating, the layer containing the metal complex compound of the present invention is preferably formed by coating. .

The element structure of the organic EL element in the present invention is a structure in which one or two or more organic layers are laminated between electrodes. Examples thereof include (i) an anode, a light emitting layer, a cathode, (ii) an anode, Hole injection / transport layer, light emitting layer, electron injection / transport layer, cathode, (iii) anode, hole injection / transport layer, light emitting layer, cathode, (iv) anode, light emitting layer, electron injection / transport layer, cathode, etc. Structure.
The metal complex compound in the present invention may be used in any of the above organic layers, and may be doped into other hole transport materials, light emitting materials, and electron transport materials. The formation method of each layer of the organic EL element is not particularly limited. In addition to the vapor deposition method, after dissolving the light emitting composition of the present invention or the compound forming the composition, various wet methods using this solution are used. Thus, a light emitting medium or a light emitting layer can be formed. It can be formed by a known method such as a solution dipping method, a spin coating method, a casting method, a bar coating method, a roll coating method or the like, an ink jet method or the like. The film thickness of each organic layer of the organic EL device of the present invention is not particularly limited. Generally, if the film thickness is too thin, defects such as pinholes are likely to occur. Conversely, if it is too thick, a high applied voltage is required and the efficiency is deteriorated. Therefore, the range of several nm to 1 μm is usually preferable.

  Examples of solvents used in preparing the luminescent solution for forming the luminescent layer include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, and other halogenated hydrocarbon solvents, dibutyl ether, Ether solvents such as tetrahydrofuran, dioxane, and anisole, alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, benzene, toluene, xylene, ethylbenzene, hexane , Hydrocarbon solvents such as octane and decane, and ester solvents such as ethyl acetate, butyl acetate and amyl acetate. Of these, halogen-based hydrocarbon solvents and hydrocarbon-based solvents are preferable. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these. In addition, the metal complex compound of the present invention may be dissolved in the luminescent solution in advance as a dopant.

  Moreover, when using the metal complex compound of this invention as a dopant, the organic EL element which can be light-emitted white is obtained by using for a light emitting layer combining with another luminescent dopant. The other light-emitting dopant may be a fluorescent light-emitting material or a phosphorescent light-emitting material, and is not particularly limited, but preferably has a maximum emission wavelength in the yellow to red region.

The electron injecting / transporting material used in the present invention is not particularly limited, and any compound that is usually used as an electron injecting / transporting material may be used. Nitrogen-containing ring derivatives, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, bis {2- (4-t-butylphenyl) -1, Examples include oxadiazole derivatives such as 3,4-oxadiazole} -m-phenylene, triazole derivatives, and quinolinol-based metal complexes. Moreover, it is preferable to use an insulator or a semiconductor as the inorganic compound constituting the electron injection / transport layer.
Moreover, when the organic EL element of this invention has an electron injection layer and / or an electron carrying layer between the said light emitting layer and a cathode, it is preferable to contain a nitrogen-containing ring derivative as a main component.
As the nitrogen-containing ring derivative, an aromatic heterocyclic compound having a hetero atom in the molecule is preferable.

As this nitrogen-containing ring derivative, what is represented by general formula (A) is preferable, for example.

R ^{A1 to} R ^A6 are each independently a hydrogen atom, a halogen atom, an oxy group, an amino group, or a hydrocarbon group having 1 to 40 carbon atoms, and these may be substituted.
Examples of the halogen atom include the same ones as described above. Examples of the amino group which may be substituted include those similar to the alkylamino group, arylamino group and aralkylamino group (arylalkyl is the same as the aromatic hydrocarbon group and alkyl group). It is done.
Examples of the hydrocarbon group having 1 to 40 carbon atoms include a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, alkoxy group, aryl group (aromatic hydrocarbon group), heterocyclic group, aralkyl group, aryloxy Group, alkoxycarbonyl group and the like. Examples of the alkyl group, alkenyl group, cycloalkyl group, alkoxy group, aryl group, heterocyclic group, aralkyl group, and aryloxy group include those described above, and the alkoxycarbonyl group is represented by -COOY '. Examples of Y ′ include those similar to the alkyl group.

M is aluminum (Al), gallium (Ga) or indium (In), and is preferably In.
L ^A in the general formula (A) is a group represented by the following general formula (A ′) or (A ″).

(Wherein R ^{A7 to} R ^A11 are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other may form a cyclic structure. R ^{A12 to} R ^A26 are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other may form a cyclic structure.)
The hydrocarbon group having 1 to 40 carbon atoms represented by R ^{A7 to} R ^A11 and R ^{A12 to} R ^{A26 in the} general formulas (A ′) and (A ″) is the same as the specific examples of R ^{A1 to} R ^A6 . Things.
In addition, as the divalent group in the case where the adjacent groups of R ^{A7 to} R ^A11 and R ^{A12 to} R ^A26 form a cyclic structure, a tetramethylene group, a pentamethylene group, a hexamethylene group, diphenylmethane-2, A 2'-diyl group, a diphenylethane-3,3'-diyl group, a diphenylpropane-4,4'-diyl group and the like can be mentioned.
Specific examples of the nitrogen-containing ring metal chelate complex represented by formula (A) are shown below, but are not limited to these exemplified compounds.

  As the nitrogen-containing ring derivative, a nitrogen-containing 5-membered ring derivative is also preferable. Examples of the nitrogen-containing 5-membered ring include an imidazole ring, a triazole ring, a tetrazole ring, an oxadiazole ring, a thiadiazole ring, an oxatriazole ring, and a thiatriazole ring. Examples of the nitrogen-containing 5-membered ring derivative include a benzimidazole ring, a benzotriazole ring, a pyridinoimidazole ring, a pyrimidinoimidazole ring, and a pyridazinoimidazole ring, and particularly preferably the following general formula (B) It is represented by

In the general formula (B), L ^B represents a divalent or higher linking group, for example, carbon, silicon, nitrogen, boron, oxygen, sulfur, metals (e.g., barium, beryllium), aromatic hydrocarbon ring, aromatic Heterocycles and the like are mentioned, and among these, a carbon atom, a nitrogen atom, a silicon atom, a boron atom, an oxygen atom, a sulfur atom, an aryl group, and an aromatic heterocyclic group are preferable, and a carbon atom, a silicon atom, an aryl group, and an aromatic group Heterocyclic groups are more preferred.
Aryl group and aromatic heterocyclic group of L ^B may have a substituent, preferably an alkyl group as a substituent, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, A cyano group and an aromatic heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group and an aromatic heterocyclic group, still more preferably an alkyl group, an aryl group, Alkoxy group, aryloxy , An aromatic heterocyclic group, particularly preferably an alkyl group, an aryl group, an alkoxy group, an aromatic heterocyclic group.
Specific examples of L ^B, are listed below.

X ^B1 in the general formula (B) represents —O—, —S— or ═N—R ^B1 . R ^B1 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.
The aliphatic hydrocarbon group for R ^B1 is a linear, branched or cyclic alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms). , For example, methyl, ethyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and an alkenyl group (preferably having 2 to 20 carbon atoms). Preferably it is a C2-C12 alkenyl group, Most preferably, it is a C2-C8 alkenyl group, for example, a vinyl, an allyl, 2-butenyl, 3-pentenyl etc.), an alkynyl group (preferably C2). -20, more preferably an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl, 3-pentynyl, etc. Mentioned are.), And, if it is an alkyl group.
The aryl group represented by R ^B1 is a monocyclic ring or a condensed ring, preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. Examples include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-trifluoromethylphenyl, pentafluorophenyl, 1-naphthyl, 2-naphthyl and the like.

The heterocyclic group of R ^B1 is a monocyclic ring or a condensed ring, preferably a heterocyclic group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 2 to 10 carbon atoms, preferably An aromatic heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Examples of this heterocyclic group include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, selenophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, Thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, Tetrazaindene, carbazole, azepine and the like, preferably, furan, thiophene, Jin, pyrazine, pyrimidine, pyridazine, triazine, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, more preferably furan, thiophene, pyridine, quinoline, and still more preferably quinoline.
Aliphatic hydrocarbon group represented by R ^B1, aryl group and heterocyclic group may have a substituent, the substituent similar to those mentioned as the substituent of the group represented by the L ^B The preferred substituents are also the same.
R ^B1 is preferably an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, more preferably an aliphatic hydrocarbon group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably carbon Or an aryl group, more preferably an aliphatic hydrocarbon group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 2 to 10 carbon atoms). It is.

X ^B1 is preferably —O— and ═N—R ^B1 , more preferably ═N—R ^B1 , and particularly preferably ═N—R ^B1 .
Z ^B1 represents an atomic group necessary for forming an aromatic ring. The aromatic ring formed by Z ^B1 may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Specific examples include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, Examples include pyrrole ring, furan ring, thiophene ring, selenophene ring, tellurophen ring, imidazole ring, thiazole ring, selenazole ring, tellurazole ring, thiadiazole ring, oxadiazole ring, pyrazole ring, preferably benzene ring, pyridine ring, A pyrazine ring, a pyrimidine ring, and a pyridazine ring, more preferably a benzene ring, a pyridine ring, and a pyrazine ring, still more preferably a benzene ring and a pyridine ring, and particularly preferably a pyridine ring.
The aromatic ring formed by Z ^B1 may further form a condensed ring with another ring and may have a substituent. The substituent is the same as those exemplified as the substituents of the group represented by the L ^B, preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano Group, a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, or a heterocyclic group, and still more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group Group, aromatic complex It is a group, particularly preferably an alkyl group, an aryl group, an alkoxy group, an aromatic heterocyclic group.
n ^B1 is an integer of 1 to 4, preferably 2 to 3.

Of the nitrogen-containing five-membered ring derivatives represented by the general formula (B), more preferably those represented by the following general formula (B ′).

In general formula (B ′), R ^B2 , R ^B3 and R ^B4 are the same as R ^B1 in general formula (B), respectively, and the preferred ranges are also the same.
Z ^B2 , Z ^B3 and Z ^B4 are the same as Z ^B1 in the general formula (B), respectively, and the preferred ranges are also the same.
L ^B2, L ^B3 and L ^B4 each represent a linking group, those divalent examples of L ^B in the general formula (B) can be mentioned, preferably a single bond, a divalent aromatic hydrocarbon ring A linking group composed of a group, a divalent aromatic heterocyclic group, and a combination thereof, and more preferably a single bond. L ^B2, L ^B3 and L ^B4 may have a substituent, examples of the substituent are the same as those exemplified as the substituents of the group represented by L ^B in the foregoing formula (B), also The same applies to preferable substituents.
Y represents a nitrogen atom, 1,3,5-benzenetriyl group, 2,4,6-triazinetriyl group or 2,4,6-pyridinetriyl group. The 1,3,5-benzenetriyl group may have a substituent at the 2,4,6-position. Examples of the substituent include an alkyl group, an aromatic hydrocarbon ring group, and a halogen atom. Can be mentioned.
Specific examples of the nitrogen-containing 5-membered ring derivative represented by the general formula (B) or (B ′) are shown below, but are not limited to these exemplified compounds.

Further, as an electron injection / transport material, an electron-deficient nitrogen-containing 5-membered ring or an electron-deficient nitrogen-containing 6-membered ring skeleton, a substituted or unsubstituted indole skeleton, a substituted or unsubstituted carbazole skeleton, a substituted or unsubstituted And a compound having a structure in which the azacarbazole skeleton is combined. Suitable electron-deficient nitrogen-containing 5-membered ring or electron-deficient nitrogen-containing 6-membered ring skeleton includes pyridine, pyrimidine, pyrazine, triazine, triazole, oxadiazole, pyrazole, imidazole, quinoxaline, pyrrole skeleton, and the like And molecular skeletons such as benzimidazole and imidazopyridine which are condensed with each other. Among these combinations, a pyridine, pyrimidine, pyrazine, and triazine skeleton, and a carbazole, indole, azacarbazole, and quinoxaline skeleton are preferable. The aforementioned skeleton may be substituted or unsubstituted.
Specific examples of such compounds are shown below.

The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. These are preferably π electron deficient nitrogen-containing heterocyclic groups.
If the electron injecting / transporting layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injecting property can be improved. As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injecting / transporting layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injecting property can be further improved.
Specifically, preferable alkali metal chalcogenides include, for example, Li ₂ O, Na ₂ S and Na ₂ Se, and preferable alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS and CaSe. Is mentioned. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl. Moreover, as a preferable alkaline earth metal halide, for example, CaF ₂ , fluorides such as BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.

The semiconductor constituting the electron injecting / transporting layer includes at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. One kind of oxide, nitride, oxynitride or the like may be used alone or in combination of two or more kinds. The inorganic compound constituting the electron injecting / transporting layer is preferably a microcrystalline or amorphous insulating thin film. If the electron transport layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced.
Examples of such inorganic compounds include the alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides described above.
Furthermore, the electron injection / transport layer may contain a reducing dopant having a work function of 2.9 eV or less. Here, the reducing dopant is defined as a substance capable of reducing the electron transporting compound. Accordingly, various materials can be used as long as they have a certain reducibility, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals. At least selected from the group consisting of oxides, halides of alkaline earth metals, oxides of rare earth metals or halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, organic complexes of rare earth metals One substance can be preferably used.

More specifically, preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), and Cs (work function: 1.95 eV) at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV) and Ba (work function: 2.52 eV) And at least one alkaline earth metal selected from the group consisting of) and having a work function of 2.9 eV is particularly preferable. Of these, a more preferred reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb and Cs, and most preferably Cs. . These alkali metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the light emission luminance and extend the life of the organic EL element.
Further, as a reducing dopant having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, Cs. And a combination of Na and K. By including Cs in combination, the reducing ability can be efficiently exhibited, and by adding to the electron injection region, the emission luminance and the life of the organic EL element can be improved.

  The light emitting layer of the organic EL device of the present invention can inject holes from the anode or the hole injection layer when an electric field is applied, and can inject electrons from the cathode or the electron injection layer. And holes) by the force of an electric field, a field for recombination of electrons and holes, and a function to connect this to light emission. The light emitting layer of the organic EL device of the present invention preferably contains at least the metal complex compound of the present invention, and may contain a host material having this metal complex compound as a dopant material. Examples of the host material include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. It is preferable that T1 (energy level of the lowest triplet excited state) of the host material is larger than T1 of the dopant material. By co-evaporating the host material and a light emitting material such as the metal complex compound, a light emitting layer in which the light emitting material is doped into the host material can be formed.

As said host material, what is represented, for example by general formula (CI) and (C-II) is preferable.
(Het-) n ¹ A (CI)
Het (-A) m ¹ (C-II)
[In the formula, Het represents a nitrogen-containing, oxygen or sulfur heteroaromatic group represented by a substituted or unsubstituted carbazolyl group, arylcarbazolyl group or carbazolylalkylene group, and A represents the following general formula ( E) is a group formed from the site represented by n ¹ and m ¹ are each an integer of 1 to 3.
(M ′) p- (L) q- (M ″) r (E)
(M ′ and M ″ are each independently a nitrogen-containing heteroaromatic ring having 2 to 40 carbon atoms to form a ring, which may or may not have a substituent. M ′ and M ″ may be the same or different. L is a single bond, an arylene group having 6 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or a heteroaromatic ring having 2 to 30 carbon atoms. And may or may not have a substituent bonded to the ring, p is 0 to 2, q is 1 to 3, and r is an integer of 0 to 2. However, p + r is 1 That's it.)]
Specific examples represented by the general formulas (CI) and (C-II) include the following structures, but are not limited to these examples.

In addition, compounds represented by the following general formulas (DI) and (D-II) can also be used as the host material. In the formula, Q ^{1 to} Q ⁴ each represent the same group as R ^{B1 in the} general formula (B), and L and q are the same as those defined in the general formula (E).

Specific examples represented by the general formulas (D-I) and (D-II) include the following structures, but are not limited to these examples.

The anode of the organic EL element plays a role of injecting holes into the hole injection / transport layer and / or the light emitting layer, and it is effective to have a work function of 4.5 eV or more. Specific examples of the anode material used in the present invention include indium tin oxide alloy (ITO), tin oxide (NESA), gold, silver, platinum, copper, and the like. The cathode is preferably made of a material having a small work function for the purpose of injecting electrons into the electron injecting / transporting layer and / or the light emitting layer. In the organic EL element, a hole injection (transport) layer may be used on the anode. Examples of the hole injecting / transporting layer include various organic compounds and polymers usually used in organic EL devices described in, for example, JP-A 63-295695 and JP-A 2-191694. Can be used. For example, aromatic tertiary amine, hydrazone derivative, carbazole derivative, triazole derivative, imidazole derivative, polyvinyl carbazole, polyethylenedioxythiophene / polysulfonic acid (PEDOT / PSS) and the like can be mentioned.
The cathode material of the organic EL element is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy, etc. Can be used.

EXAMPLES Next, although this invention is demonstrated in more detail using an Example, it is not limited to these Examples.
Synthesis Example 1 (Synthesis of metal complex compound 3)
Metal complex compound 3 was synthesized by the following route.

(1) Synthesis of Bfb 39 mmol (7.52 g) of 1-bromo-2,4-difluorobenzene was placed in a 100 ml flask and heated to 60 ° C. Next, after adding 0.15 g of iron, 39 mmol (6.23 g) of bromine was added dropwise over 3 hours while maintaining the temperature at 60 ° C. After completion of dropping, the reaction was further carried out at 60 ° C. for 2 hours.
The resulting reaction solution was cooled to room temperature, poured into a cold aqueous sodium hydroxide solution, and extracted with hexane. The obtained organic layer was washed with pure water and saturated brine, dehydrated with anhydrous sodium sulfate, and the solvent was removed. The obtained residue was purified by silica gel chromatography (developing solvent hexane) to obtain 8.81 g of Bfb as a colorless oil (yield 84%).
¹ H-NMR (CDCl ₃ ): δ 7.70 (t, 1H, J = 7.2Hz), 6.92 (t, 1H, J = 8.0Hz)
(2) Synthesis of Fppy In a 500 ml three-necked flask, 77 mmol (10.7 g) of 4-fluorophenylboronic acid, 70 mmol (11.0 g) of 2-bromopyridine, 1.4 mmol (1.6 g) of tetrakistriphenylphosphine palladium (0) ) 22 g of 2M aqueous sodium carbonate solution and 140 ml of 1,2-dimethoxyethane were added, and the system was purged with nitrogen. The mixture was heated to reflux for 9 hours with stirring, cooled to room temperature, extracted by adding water and ethyl acetate, and the organic layer was dried over magnesium sulfate.
After filtration, the solution was concentrated to give an orange slurry material. Purification by a silica gel column (developing solvent: dichloromethane: hexane 1: 2 to 2: 1) yielded Fppy (9.7 g, yield 80%).
¹ H-NMR (CDCl ₃ ): δ 8.68 (d, 1H, J = 5.7 Hz), 8.00-7.97 (m, 2H), 7.75 (t, 1H, J = 7.7 Hz), 7.68 (d, 1H, J = 8.0Hz), 7.24-7.22 (m, 1H), 7.16 (t, 2H, J = 8.6Hz)

(3) Synthesis of Fpyb A 200 ml three-necked flask was replaced with nitrogen, 207 mmol (8.78 g) of lithium chloride and 1.61 mmol (1.1 g) of bistriphenylphosphine palladium dichloride were added, and the atmosphere was replaced with nitrogen again. Thereto, 80 ml of toluene and 20.7 mmol (5.62 g) of Bfb were added. Further, 62.1 mmol (15 g) of trimethyl (2-pyridyl) tin was added dropwise, and the mixture was heated to reflux for 3 days under a nitrogen stream.
After standing to cool, 150 ml of saturated aqueous potassium fluoride solution was added and stirred for 30 minutes. The solid was removed by filtration, and extracted with methylene chloride and 5% aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated by adding anhydrous sodium sulfate. The brown solid obtained after removing the solvent under reduced pressure was washed with ether to obtain a white solid of Fpyb (4.3 g, yield 78%).
¹ H-NMR (CDCl ₃ ): δ 8.66 (d, 2H, J = 5.2 Hz), 8.55 (t, 1H, J = 8.9 Hz), 7.72-7.68 (m, 4H), 7.21-7.19 (m, 2H), 6.97 (t, 1H, J = 10.9Hz)
¹⁹ F-NMR (CDCl ₃ ): δ-112.95
(4) Synthesis of FpybIr To a 100 ml two-necked flask were added 1.33 mmol (0.469 g) of iridium chloride hydrate, 1.86 mmol (0.5 g) of Fpyb and 20 ml of 2-ethoxyethanol, and 20 hours under a nitrogen stream. The mixture was heated and stirred under reflux. After allowing to cool, the solvent was removed by filtration to obtain a yellow solid (0.51 g, yield 73%).
(5) Synthesis of Metal Complex Compound 3 FpybIr 0.283 mmol (0.3 g), Fppy 0.283 mmol (0.49 g), and glycerol 10 ml were added to a 100 ml eggplant type flask, and microwave irradiation was performed for 6 minutes under a nitrogen stream. Heated to reflux. After standing to cool, water was added and the resulting precipitate was collected by filtration and washed with hexane. Metal complex compound 3 was obtained as a yellow solid (0.221 g, yield 58%).
¹ H-NMR (CDCl ₃ ): δ 10.08 (d, 1H, J = 5.2 Hz), 8.10 (d, 2H, J = 8.0 Hz), 8.00-7.99 (m, 2H), 7.62 (t, 2H, J = 8.6Hz), 7.63-7.61 (m, 3H), 6.85 (t, 2H, J = 6.6Hz), 6.79 (t, 1H, J = 11.5Hz), 6.47 (t, 1H, J = 8.6Hz) , 5.72 (d, 1H, J = 10.3Hz)
Anal.calcd for C ₂₇ H ₁₆ N ₃ F ₃ IrCl: C, 48.61; H, 2.42; N, 6.30 Found: C, 48.35; H, 2.42; N, 6.10

Synthesis Example 2 (Synthesis of metal complex compound 4)
According to the synthesis route shown in Synthesis Example 1, metal complex compound 3 was synthesized.
Next, 0.3 mmol (0.2 g) of metal complex compound 3, 3.0 mmol (0.194 g) of potassium cyanide and 10 ml of methanol were added to a 50 ml eggplant-shaped flask, and the mixture was heated to reflux for 1 hour under a nitrogen stream.
After allowing to cool, the solvent was removed under reduced pressure, pure water was added, and the precipitate produced by filtration was collected and washed with hexane. Furthermore, purification was performed by silica gel column chromatography (developing solvent: chloroform) to obtain metal complex compound 4 as a yellow solid (0.135 g, yield 70%).
¹ H-NMR (CDCl ₃ ): δ 10.02 (d, 1H, J = 4.6 Hz), 8.13 (d, 2H, J = 8.0 Hz), 8.02 (d, 2H, 4.0), 7.66-7.61 (m, 5H), 7.50 (q, 1H, J = 4.8Hz), 6.85-6.81 (m, 3H), 6.51 (t, 1H, J = 8.6Hz), 5.70 (d, 1H, J = 9.2Hz)
Anal.calcd for C ₂₈ H ₁₆ N ₄ F ₃ Ir: C, 51.14; H, 2.45; N, 8.52 Found: C, 51.12; H, 2.52; N, 8.26
FT-IR (KBr): 2105 cm ^-1 [ν (CN)]

Synthesis Example 3 (Synthesis of metal complex compound 5)
Metal complex compound 5 was synthesized by the following route. Compounds Bfb, Fpyb, and FpybIr were synthesized in the same manner as in Synthesis Example 1.

(1) Synthesis of dFppy After putting 63.3 mmol (10 g) of 2,4-difluorophenylboronic acid and 1.73 mmol (2.0 g) of tetrakistriphenylphosphine palladium (0) in a 1000 ml flask, 2-Dimethoxyethane (500 ml), 1.3 M aqueous sodium carbonate solution (120 ml), and then 2-bromopyridine (63.3 mmol, 10 g) were added, and the mixture was reacted under reflux for 8 hours.
The solvent was distilled off from the obtained reaction solution, and ether extraction was performed. The separated organic layer was washed twice with water and dried over magnesium sulfate. The oily substance obtained after concentration was purified by silica column chromatography (developing solvent: methylene chloride: hexane = 1: 1) to obtain dFppy as a yellow oil (8.0 g, yield 67%).
¹ H-NMR (CO (CD ₃ ) ₂ -d6): δ 8.71 (d, 1H, J = 4.6 Hz), 8.11 (q, 1H, J = 8.0 Hz), 7.88 (t, 1H, J = 7.7 Hz), 7.81 (d, 1H, J = 8.0Hz), 7.36 (t, 1H, J = 6.0Hz), 7.16-7.14 (m, 2H)
(2) Synthesis of Metal Complex Compound 5 FpybIr 0.094 mmol (0.1 g), dFppy 0.934 mmol (0.18 g) and glycerol 10 ml were added to a 100 ml eggplant type flask and heated to reflux for 26 hours. After cooling, water was added, and the resulting precipitate was collected by filtration and washed with hexane. Metal complex compound 5 was obtained as a yellow solid (0.04 g, yield 65%).
¹ H-NMR (CDCl ₃ ): δ 10.15 (d, 1H, J = 4.0 Hz), 8.46 (d, 1H, J = 8.0 Hz), 8.11 (d, 2H, J = 8.6 Hz), 8.02 (t , 1H, J = 7.7Hz), 7.64 (t, 2H, J = 8.0Hz), 7.56 (t, 1H, J = 6.3Hz), 7.52 (d, 2H, J = 5.7Hz), 6.88 (t, 2H , J = 6.9Hz), 6.79 (t, 1H, J = 11.5Hz), 6.25 (t, 1H, J = 11.2Hz), 5.56 (d, 1H, J = 9.7Hz)

Synthesis Example 4 (Synthesis of metal complex compound 6)
According to the synthesis route shown in Synthesis Example 3, metal complex compound 5 was synthesized.
Next, 0.3 mmol (0.2 g) of metal complex compound 5, 3.0 mmol (0.194 g) of potassium cyanide and 10 ml of methanol were added to a 50 ml eggplant-shaped flask, and the mixture was heated to reflux for 1 hour in a nitrogen stream.
After allowing to cool, the solvent was removed under reduced pressure, pure water was added, and the precipitate produced by filtration was collected and washed with hexane. Furthermore, purification was performed by silica gel column chromatography (developing solvent: chloroform) to obtain metal complex compound 6 as a yellow solid (0.127 g, yield 63%).

Synthesis Example 5 (Synthesis of metal complex compound 7)
Metal complex compound 7 was synthesized by the following route. Compound FpybIr was synthesized in the same manner as in Synthesis Example 1.

(1) Synthesis of pmi In a 50 ml eggplant flask, 13.8 mmol (2.0 g) of 1-phenylimidazole and 30.5 mmol (1.9 ml) of methyl iodide were placed in 15 ml of toluene at 30 ° C. For 24 hours. The product was collected by filtration and washed with toluene to give pmi as a white solid (3.65 g, 92% yield).
¹ H-NMR (CDCl ₃ ): δ 10.55 (s, 1H), 7.78-7.76 (m, 2H), 7.61-7.56 (m, 5H), 4.29 (s, 3H)
(2) Synthesis of Metal Complex Compound 7 FpybIr 0.094 mmol (0.1 g), pmi 0.282 mmol (0.081 g), silver oxide 1.22 mmol (0.283 g) and 2-ethoxyethanol 25 ml in a 50 ml eggplant flask. And heated under reflux for 6 hours under a nitrogen stream.
After allowing to cool, the solvent was removed under reduced pressure, dissolved in methylene chloride, and filtered through celite. The solid after removing the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 100: 1). Further, recrystallization was performed with methylene chloride / chloroform / hexane to obtain a metal complex compound 7 (82 mg, 67% yield).
Anal.Calcd for C ₂₆ H ₁₉ N ₅ F ₂ ClIr: C, 47.81; H, 2.93; N, 8.58 Found: C, 47.66; H, 2.53; N, 8.18
¹ H-NMR (CDCl ₃ ): δ 8.05 (d, 2H, J = 8.0 Hz), 7.88 (d, 2H, J = 5.2 Hz), 7.62 (d, 1H, J = 2.3 Hz), 7.56 (t , 2H, J = 7.7Hz), 7.24 (d, 2H, J = 2.3Hz), 7.04 (d, 1H, J = 9.2Hz), 6.77 (t, 2H, J = 6.6 Hz), 6.71 (t, 1H , J = 6.9Hz), 6.47 (t, 1H, J = 7.4Hz), 5.99 (d, 1H, J = 5.99Hz)
¹⁹ F-NMR (CDCl ₃ ): δ-108.62

Synthesis Example 6 (Synthesis of metal complex compound 8)
The metal complex compound 7 was synthesized according to the synthesis route shown in Synthesis Example 5.
Next, 0.077 mmol (0.05 g) of metal complex compound 7, 0.766 mmol (0.05 g) of potassium cyanide, and 10 ml of methanol were placed in a 50 ml eggplant flask and heated to reflux for 14 hours under a nitrogen stream. After allowing to cool, the solvent was removed under reduced pressure, pure water was added, the mixture was filtered, and washed with hexane. Furthermore, purification was performed by silica gel column chromatography (developing solvent: methylene chloride: methanol = 25: 1) to obtain metal complex compound 8 as a light yellow solid (33 mg, yield 67%).
Anal.calcd for C ₂₇ H ₁₉ N ₅ F ₂ Ir: C, 50.38; H, 2.98; N, 10.88 Found: C, 50.20; H, 2.69; N, 10.52
¹ H-NMR (CDCl ₃ ): δ 8.06 (d, 2H, J = 8.6 Hz), 7.83 (d, 2H, J = 5.7 Hz), 7.62 (s, 1H), 7.58 (t, 2H, J = 8.0Hz), 7.23 (s, 1H), 7.09 (d, 1H, J = 8.0Hz), 6.82-6.78 (m, 2H), 6.73 (t, 2H, J = 6.6Hz), 6.53 (t, 1H, J = 7.2Hz), 6.02 (d, 1H, J = 7.4Hz)
¹⁹ F-NMR (CDCl ₃ ): δ-108.49
FT-IR (KBr): 2103cm ^-1 [ν (CN)]

Synthesis Example 7 (Synthesis of metal complex compound 9)
Metal complex compound 9 was synthesized by the following route. Compound FpybIr was synthesized in the same manner as in Synthesis Example 1.

(1) Synthesis of CFppy In a 100 ml two-necked flask, 13 mmol (1.49 g) of 2-chloropyridine, 16 mmol (3.0 g) of 2-trifluoromethylphenylboronic acid, 20 ml of 1,2-dimethoxyethane, 2M aqueous potassium carbonate solution 12 ml and tetrakistriphenylphosphine palladium (0) 0.65 mmol (0.751 g) were added and the mixture was refluxed for 19 hours. After cooling, the mixture was extracted with ethyl acetate and dehydrated with sodium sulfate, and then the solvent was removed. Purification was performed by distillation under reduced pressure to obtain CFppy (1.83 g, yield 63%).
¹ H-NMR (CDCl ₃ ): δ 8.73 (d, 1H, J = 4.6 Hz), 8.28 (s, 1H), 8.18 (d, 1H, J = 7.4 Hz), 7.82-7.76 (m, 2H) , 7.67 (d, 1 H, J = 7.4Hz), 7.60 (t, 1H, J = 7.7Hz), 7.30-7.29 (m, 1H)
(2) Synthesis of Metal Complex Compound 9 FpybIr 0.189 mmol (0.2 g), CFppy 1.89 mmol (0.421 g), and 10 ml of glycerol were placed in a 100 ml eggplant type flask and subjected to microwave irradiation for 12 minutes under a nitrogen stream. Heated to reflux. After allowing to cool, water was added, and the resulting precipitate was collected by filtration and washed with hexane. Purification by silica gel column chromatography (developing solvent chloroform) and recrystallization with methylene chloride / hexane gave metal complex compound 9 as a white yellow solid (0.216 g, yield 80%).
¹ H-NMR (CDCl ₃ ): δ 10.1 (d, 1H, J = 6.3 Hz), 8.15 (d, 1H, J = 6.3 Hz), 8.10 (d, 2H, J = 8.0 Hz), 8.06 (t , 1H, J = 8.0Hz), 7.80 (s, 1H), 7.66-7.61 (m, 3H), 7.53 (d, 2H, J = 5.7Hz), 6.86 (t, 2H, J = 6.6Hz), 6.83 -6.78 (m, 2H), 6.22 (d, 1H, J = 9.7Hz)

Synthesis Example 8 (Synthesis of metal complex compound 10)
According to the synthesis route shown in Synthesis Example 7, metal complex compound 9 was synthesized.
Next, 0.301 mmol (0.216 g) of metal complex compound 9, 3.0 mmol (0.194 g) of potassium cyanide and 10 ml of methanol were placed in a 50 ml eggplant-shaped flask, and the mixture was heated to reflux for 1 hour in a nitrogen stream. After allowing to cool, the solvent was removed under reduced pressure, pure water was added, and the precipitate produced by filtration was collected and washed with hexane. Furthermore, purification was performed by silica gel column chromatography (developing solvent: methylene chloride: methanol = 50: 1) to obtain the metal complex compound 10 as a white yellow solid (0.11 g, yield 52%).
Anal.calcd for C ₂₉ H ₁₆ N ₅ F ₄ Ir: C, 49.22; H, 2.28; N, 7.92 Found: C, 49.34; H, 2.31; N, 7.68
¹ H-NMR (CDCl ₃ ): δ 10.08 (d, 1H, J = 5.7 Hz), 8.17 (d, 1H, J = 8.0 Hz), 8.13-8.08 (m, 3H), 7.83 (s, 1H) , 7.66-7.58 (m, 5H), 6.88-6.82 (m, 4H), 6.19 (d, 1H, J = 8.0Hz)
¹⁹ F-NMR (CDCl ₃ ): δ-62.10 (CFppy), -107.62 (Fpyb)
FT-IR (KBr): 2112 cm ^-1 [ν (CN)]

Synthesis Example 9 (Synthesis of metal complex compound 11)
Metal complex compound 11 was synthesized by the following route.

(1) Synthesis of Bcfb Copper bromide (II) 4.79 mmol (1.07 mg) and acetonitrile 15 ml were placed in a three-necked flask and 6.4 mmol (0.844 ml) of t-butyl nitrite at 0 ° C. under nitrogen. -Amino-5-bromobenzotrifluoride 4.16mmol (1.0g) was dripped and it stirred for 1.5 hours. Then, it returned to room temperature and stirred for 16 hours.
The resulting solution was concentrated in half, washed with 1N hydrochloric acid and extracted with ether. After dehydrating the organic layer, the solvent was removed under reduced pressure, and purification was performed with a silica gel column (developing solvent hexane) to obtain Bcfb as an orange oil (0.84 g, yield 58%).
¹ H-NMR (CD ₃ CN): δ 8.04 (s, 1H), 7.88 (s, 2H)
(2) Synthesis of CFpyb It was synthesized in the same manner as the synthesis of Fpyb in Synthesis Example 1. However, Bcfb was used as a raw material bromide, and tri-n-butyl (2-pyridyl) tin was used as a tin compound. Purification was performed by silica gel column chromatography (developing solvent hexane: ether = 4: 1). (0.64 g, 26% yield)
¹ H-NMR (CDCl ₃ ): δ 8.84 (s, 1H), 8.75 (d, 2H, J = 5.7 Hz), 8.34 (s, 2H), 7.89 (d, 2H, J = 8.0 Hz), 7.82 (t, 2H, J = 7.7Hz), 7.32 (t, 2H, J = 6.0Hz)
(3) Synthesis of CFpybIr 0.284 mmol (0.1 g) of iridium chloride hydrate and 10 ml of 2-ethoxyethanol were placed in a 100 ml two-necked flask and stirred at 110 ° C. under a nitrogen stream. When the temperature rose, 0.397 mmol (0.119 g) of CFpyb was added and stirred with heating for 20 hours. After allowing to cool, the mixture was washed with filtered methanol and ether to give an orange solid (0.103 g, yield 65%).
(4) Synthesis of Metal Complex Compound 11 CFpybIr 0.089 mmol (0.1 g), Fppy 0.712 mmol (0.123 g), and glycerol 10 ml were placed in a 100 ml eggplant-shaped flask and subjected to microwave irradiation for 12 minutes under a nitrogen stream. Heated to reflux. After allowing to cool, water was added and the resulting precipitate was collected by filtration and washed with hexane to give a yellow powder. Purification was performed by silica gel column chromatography (developing solvent: methylene chloride: methanol = 50: 1) and recrystallization from methylene chloride / hexane to obtain a yellow solid of metal complex compound 11 (67 mg, yield 54%).
¹ H-NMR (CDCl ₃ ): δ 10.09 (d, 1H, J = 5.7 Hz), 8.02-8.00 (m, 4H), 7.95 (d, 2H, J = 8.0 Hz), 7.67 (t, 2H, J = 7.7Hz), 7.64 (d, 2H, J = 5.7Hz), 7.60-7.55 (m, 2H), 6.92 (t, 2H, J = 6.6Hz), 6.45 (t, 1H, J = 8.6Hz) , 5.55 (d, 1H, J = 9.7Hz)
¹⁹ F-NMR (CDCl ₃ ): δ-60.82 (CF ₃ pyb), -100.71 (fppy)

Synthesis Example 10 (Synthesis of metal complex compound 12)
The metal complex compound 11 was synthesized according to the synthesis route shown in Synthesis Example 9.
Next, 0.086 mmol (60 mg) of the metal complex compound 11 was used as a raw material, and synthesized in the same manner as the metal complex compound 4. Purification was performed by silica gel column chromatography (developing solvent: methylene chloride: methanol = 50: 1) to obtain a white yellow solid of metal complex compound 12 (37 mg, yield 63%).
¹ H-NMR (CDCl ₃ ): δ 10.04 (d, 1H, J = 5.2 Hz), 8.04-8.03 (m, 4H), 7.97 (d, 2H, J = 8.0 Hz), 7.72-7.68 (m, 4H), 7.62 (t, 1H, J = 6.9Hz), 7.51 (t, 1H, J = 7.2Hz), 6.91 (t, 2H, J = 6.0Hz), 6.48 (t, 1H, J = 8.9Hz) , 5.50 (d, 1H, J = 9.2Hz)

Synthesis Example 11 (Synthesis of metal complex compound 29)
Metal complex compound 29 was synthesized by the following route.

(1) Synthesis of Ifb A 500 ml three-necked flask was purged with nitrogen, 38 mmol (3.1 g) of N-methylimidazole and 50 ml of tetrahydrofuran were added, and 27.5 ml (44 mmol) of 1.6 M n-butyllithium was added at -70 ° C. added. After stirring for 2 hours, 44 mmol (6.0 g) of anhydrous zinc chloride suspended in tetrahydrofuran was added dropwise, and the mixture was stirred for 1 hour and returned to room temperature. Further, a solution prepared by dissolving 0.504 mmol (0.412 g) of 1,1′-bis (diphenylphosphino) ferrocene palladium (II) dichloride and 25.2 mmol (6.88 g) of Bfb in 20 ml of tetrahydrofuran was added for 1 hour. Half refluxed. After slightly cooling, 76 mmol (10.4 g) of anhydrous zinc chloride was added, and the mixture was further refluxed for 5 days.
The obtained reaction solution was put in 236 mmol (88 g) aqueous solution (1 L) of ethylenediamine N, N, N ′, N′-tetraacetic acid disodium salt anhydride and adjusted to pH 8 with 10% aqueous sodium carbonate solution. The organic substance was extracted with methylene chloride, dehydrated with sodium sulfate, and the solvent was removed. Purification was performed with a silica gel column (developing solvent: acetone) to obtain a yellow solid. By further sublimation, a white solid of Ifb was obtained (10.2 g, yield 46%).
¹ H-NMR (CDCl ₃ -d): δ 7.84 (t, 1H, J = 7.7Hz), 7.16 (d, 1H, J = 1.1Hz), 7.03-7.01 (m, 2H), 3.62 (d, (3H, J = 2.3Hz)
(2) Synthesis of Pyifb A 500 ml three-necked flask was replaced with nitrogen, 45.3 mmol (1.92 g) of lithium chloride, 11.3 mmol (3.1 g) of Ifb, 0.354 mmol (0.248 g) of bistriphenylphosphine palladium dichloride, tributyl 13.6 mmol (5.0 g) of (2-pyridyl) tin and 40 ml of toluene were added, and the mixture was heated to reflux for 6 days.
Saturated potassium fluorinated aqueous solution was added after standing_to_cool, and it stirred for 3 hours. The solid was removed by filtration, extracted with 150 ml of methylene chloride and 5% aqueous sodium hydrogen carbonate solution, and dehydrated by adding anhydrous sodium sulfate to the organic layer. The brown oil obtained after removing the solvent under reduced pressure was purified by a silica column to obtain a yellow oil of Pyifb (2.4 g, yield 78%).
¹ H-NMR (Acetone-d6): δ8.72 (q, 1H, J = 2.1 Hz), 8.29 (t, 1H, J = 8.9 Hz), 7.93-7.89 (m, 2H), 7.42-7.39 (m , 1H), 7.34 (t, 1H, J = 11.2Hz), 7.25 (d, 1H, J = 1.1Hz), 7.06 (d, 1H, J = 1.1Hz), 3.70 (d, 3H, J = 1.7Hz) )
(3) Synthesis of PyifbIr To a 100 ml eggplant flask were added 5.9 mmol (2.07 g) of iridium chloride hydrate, 8.8 mmol (2.4 g) of Pyifb and 30 ml of 2-ethoxyethanol, and the mixture was refluxed for 24 hours under a nitrogen stream. The mixture was stirred under heating. After allowing to cool, the product was filtered and washed with hexane and ether to give a yellow solid (2.91 g, 91% yield).
(4) Synthesis of metal complex compound 29 PyifbIr 0.46 mmol (0.5 g), Fppy 2.3 mmol (0.4 g), and ethylene glycol 25 ml were added to a 100 ml eggplant-shaped flask, and 1 was irradiated by microwave irradiation in a nitrogen stream. Heated to reflux for 3 minutes. After allowing to cool, water was added, and the resulting precipitate was filtered with a centrifuge and washed with hexane. Furthermore, it refine | purified by the silica column (developing solvent methanol: dichloromethane = 1: 25), and obtained the metal complex compound 29 as a yellow solid (0.289g, 47% of yield).
¹ H-NMR (CDCl ₃ -d): δ 10.06 (d, 1H, J = 5.2Hz), 8.12 (d, 1H, J = 8.6Hz), 7.95-7.92 (m, 2H), 7.62-7.54 ( m, 3H), 7.47 (t, 1H, J = 6.0Hz), 6.83 (t, 1H, J = 6.6Hz), 6.76 (t, 1H, J = 11.7Hz), 6.65 (d, 1H, J = 1.7 Hz), 6.45 (t, 1H, J = 8.6Hz), 6.21 (d, 1H, J = 1.7Hz), 5.63 (d, 1H, J = 10.0Hz), 4.09 (d, 3H, J = 4.6Hz)

Synthesis Example 12 (Synthesis of metal complex compound 30)
According to the synthesis route shown in Synthesis Example 11, metal complex compound 29 was synthesized.
Next, 0.45 mmol (0.3 g) of metal complex compound 29, 4.5 mmol (0.292 g) of potassium cyanide and 40 ml of methanol were added to a 100 ml eggplant type flask, and the mixture was refluxed under a nitrogen stream. The product was collected by filtration and washed with hexane to give a yellow powder. Purification by silica gel column chromatography (developing solvent: methanol: methylene chloride = 1: 25) gave a yellow powder of metal complex compound 30 (0.113 g, yield 38%).
¹ H-NMR (CDCl ₃ -d): δ8.14 (d, 1H, J = 8.6Hz), 7.96-7.95 (m, 2H), 7.70 (d, 1H, J = 5.2Hz) 7.62-7.59 (m , 2H), 7.42 (t, 1H, J = 5.7Hz), 6.82-6.79 (m, 2H), 6.67 (d, 1H, J = 1.1Hz), 6.49 (t, 1H, J = 8.6Hz), 6.26 (d, 1H, J = 1.7Hz), 5.64 (d, 1H, J = 9.5Hz), 4.10 (d, 3H, J = 5.2Hz)

Synthesis Example 13 (Synthesis of metal complex compound 23)
Metal complex compound 23 was synthesized by the following route.

(1) Synthesis of t-BupySn A 500 ml three-necked flask was purged with nitrogen, 136 mmol (13.8 ml) of 2-dimethylaminoethanol and 170 ml of hexane were added, and 170 ml (272 mmol) of 1.6 M n-butyllithium was added at 0 ° C. Added dropwise. After maintaining at 0 ° C. and stirring for 15 minutes, a solution of 68 mmol (10 ml) of 4-t-butylpyridine in 30 ml of hexane was added dropwise, and the mixture was further stirred at 0 ° C. for 1 hour. Then, it cooled to -78 degreeC, 154 mmol (50g) of trimethyltin chloride was dripped, it stirred for 5 hours, the ice bath was removed, and it was made to react for 12 hours.
Water was added to the reaction solution, extracted with ether, and the solvent was removed. Purification by silica gel column chromatography (developing solvent hexane: ethyl acetate = 5: 1) gave t-BupySn (23 g, yield 80%).
(2) Synthesis of tBuCFpyb A 100 ml three-necked flask was replaced with nitrogen, and lithium chloride 15.8 mmol (0.67 g), Bcfb 1.58 mmol (0.48 g), bistriphenylphosphine palladium dichloride 0.04 mmol (0.029 g), t -BupySn 4.97 mmol (2.1 g) and 35 ml of toluene were added, and the mixture was heated to reflux for 24 hours.
Saturated potassium fluorinated aqueous solution was added after standing_to_cool, and it stirred for 30 minutes. The solid was removed by filtration, extracted with 150 ml of methylene chloride and 5% aqueous sodium hydrogen carbonate solution, and dehydrated by adding anhydrous sodium sulfate to the organic layer. The brown oil obtained after removing the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 10: 1) to obtain a brown oil of tBuCFpyb (0.28 g, yield 38%).
¹ H-NMR (CDCl ₃ -d): δ8.75 (s, 1H), 8.65 (d, 2H, J = 5.0 Hz), 8.29 (s, 2H), 7.81 (d, 2H, J = 2.0 Hz) , 7.31 (dd, 2H, J = 5.0Hz), 1.40 (s, 18H)
(3) Synthesis of tBuCFpybIr To a 100 ml eggplant flask were added 2.25 mmol (0.67 g) of iridium chloride hydrate, 3.15 mmol (1.3 g) of tBuCFpyb and 40 ml of 2-ethoxyethanol, and the mixture was refluxed for 14 hours under a nitrogen stream. The mixture was stirred under heating. After cooling, the product was filtered and washed with methanol to give an orange solid (0.98 g, 64% yield).
(4) Synthesis of Metal Complex Compound 23 To a 200 ml eggplant type flask, 0.72 mmol (0.98 g) of tBuCFpybIr, 7.26 mmol (1.25 g) of Fppy and 50 ml of glycerin were added, and heated for 15 minutes by microwave irradiation under a nitrogen stream. Refluxed. After allowing to cool, water was added, and the resulting precipitate was filtered with a centrifuge and washed with hexane. Furthermore, it refine | purified by the silica column (developing solvent methanol: dichloromethane = 1: 25), and obtained the metal complex compound 23 as a yellow solid (1.19 g, 100% of yield).
FD-MS m / z = 811 (811.3 required for C ₃₆ H ₃₃ ClF ₄ IrN ₃ )

Synthesis Example 14 (Synthesis of metal complex compound 24)
According to the synthesis route shown in Synthesis Example 13, metal complex compound 23 was synthesized.
Then, 1.47 mmol (1.19 g) of metal complex compound 23, 14.6 mmol (0.955 g) of potassium cyanide and 50 ml of methanol were added to a 100 ml eggplant-shaped flask and refluxed under a nitrogen stream. The product was collected by filtration and washed with hexane to give a yellow powder. Purification by silica gel column chromatography (developing solvent: chloroform) gave a yellow powder of metal complex compound 24 (0.7 g, yield 60%).
FD-MS m / z = 802 (801.9 required for C37H33F4IrN4)

Synthesis Example 15 (Synthesis of metal complex compound 37)
Metal complex compound 37 was synthesized by the following route.

(1) Synthesis of i-PrpyBr A 500 ml three-necked flask was purged with nitrogen, and 100 mmol (10.1 ml) of 2-dimethylaminoethanol and 100 ml of hexane were added, and 125 ml (200 mmol) of 1.6 M n-butyllithium at −10 ° C. Was added dropwise. After maintaining at −10 ° C. and stirring for 1.5 hours, a 20 ml hexane solution of 50 mmol (6.5 ml) of 4-i-propylpyridine was added dropwise. Then, it cooled to -78 degreeC, the THF50ml solution of carbon tetrabromide 125mmol (41.4g) was dripped, the ice bath was removed, and it was made to react for 15 hours.
Water was added to the reaction solution, extracted with methylene chloride, and the solvent was removed. Purification by silica gel column chromatography (developing solvent hexane: ethyl acetate = 8: 2) gave i-PrpyBr (6.0 g, yield 60%).
(2) Synthesis of i-PrpySn A 300 ml three-necked flask was purged with nitrogen, 29.3 mmol (5.87 g) of i-PrpyBr and 110 ml of THF were added, and 20 ml of 1.6M n-butyllithium was added at −78 ° C. (32. 9 mmol) was added dropwise. After stirring at −78 ° C. for 30 minutes, 29.7 mmol (8.1 ml) of tributyltin chloride was added dropwise. Thereafter, the ice bath was removed and the reaction was allowed to proceed for 7 hours. Water was added to the reaction solution, extracted with methylene chloride, and the solvent was removed. Purification by silica gel column chromatography (developing solvent hexane: ethyl acetate = 5: 1) gave i-PrpySn (10.1 g, yield 63%).
(3) Synthesis of iPrFpyb A 100 ml three-necked flask was replaced with nitrogen, and 36 mmol (1.52 g) of lithium chloride, 3.67 mmol (1.0 g) of Bfb, 0.1 mmol (0.07 g) of bistriphenylphosphine palladium dichloride, i-PrpySn 11.0 mmol (4.52 g) and 40 ml of toluene were added, and the mixture was heated to reflux for 13 hours.
Saturated potassium fluorinated aqueous solution was added after standing_to_cool, and it stirred for 1 hour. The solid was removed by filtration and extracted with 250 ml of methylene chloride and 5% aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated by adding anhydrous magnesium sulfate. The brown oil obtained after removing the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 8: 2) to obtain a brown oil of iPrFpyb (0.62 g, yield 48%).
FD-MS m / z = 352 (352.4 required for C22H22F2N2)
(4) Synthesis of iPrFpybIr To a 200 ml eggplant flask, 3.59 mmol (1.07 g) of iridium chloride hydrate, 3.94 mmol (1.39 g) of iPrFpyb and 50 ml of 2-ethoxyethanol were added and refluxed for 16 hours under a nitrogen stream. The mixture was stirred under heating. After standing to cool, the product was filtered and washed with methanol to give an orange solid (1.74 g, yield 79%).
(5) Synthesis of metal complex compound 37 Into a 200 ml eggplant-shaped flask were added 1.4 mmol (1.72 g) of iPrFpybIr, 14.0 mmol (2.42 g) of Fppy and 50 ml of glycerin, and heated for 1 hour by microwave irradiation in a nitrogen stream. Refluxed. After allowing to cool, water was added, and the resulting precipitate was filtered with a centrifuge and washed with hexane. Furthermore, it refine | purified by the silica column (developing solvent methanol: dichloromethane = 1: 25), and obtained the metal complex compound 37 as a yellow solid (2.23 g, 100% of yield).
FD-MS m / z = 751 (751.2 required for C33H28ClF3IrN3)

Synthesis Example 16 (Synthesis of metal complex compound 38)
According to the synthesis route shown in Synthesis Example 15, metal complex compound 37 was synthesized.
Subsequently, 2.66 mmol (1.66 g) of metal complex compound 37, 26.6 mmol (1.73 g) of potassium cyanide and 90 ml of methanol were added to a 100 ml eggplant type flask, and the mixture was refluxed for 14 hours under a nitrogen stream. The product was collected by filtration and washed with hexane to give a yellow powder. Purification by silica gel column chromatography (developing solvent chloroform) gave a yellow powder of metal complex compound 38 (1.1 g, yield 89%).
FD-MS m / z = 742 (741.8 required for C34H28F3IrN4)

Synthesis Example 17 (Synthesis of metal complex compound 15)
Metal complex compound 15 was synthesized by the following route.

(1) Synthesis of t-BuFpyb A 100 ml three-necked flask was purged with nitrogen, and lithium chloride 94.5 mmol (4.0 g), Bfb 9.45 mmol (2.58 g), bistriphenylphosphine palladium dichloride 0.245 mmol (0.173 g) , T-BupySn 37.8 mmol (16.0 g) and 20 ml of toluene were added, and the mixture was heated to reflux for 5 days.
After standing to cool, saturated potassium fluorinated aqueous solution was added and stirred for 30 minutes. The solid was removed by filtration and extracted with methylene chloride and 5% aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated by adding anhydrous magnesium sulfate. The yellowish green oil obtained after removing the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 8: 2) to obtain a light yellow oil of t-BuFpyb (0.46 g, yield). 13%).
¹ H-NMR (CDCl ₃ -d): δ8.61 (d, 2H, J = 5.3 Hz), 8.45 (t, 1H, J = 8.9 Hz), 7.72 (d, 2H, J = 0.9 Hz), 7.26 (dd, 2H, J = 5.3, 1.8Hz), 7.03 (t, 1H, JH-F = 10.5Hz), 1.36 (s, 18H)
(2) Synthesis of t-BuFpybIr To a 100 ml eggplant flask was added 2.25 mmol (0.794 g) of iridium chloride hydrate, 3.15 mmol (1.2 g) of t-BuFpyb and 50 ml of 2-ethoxyethanol, and under a nitrogen stream. The mixture was heated and stirred under reflux for 4 hours and a half. After allowing to cool, the product was filtered and washed with hexane to give an orange solid (1.34 g, 93% yield).
(3) Synthesis of metal complex compound 15 To a 100 ml eggplant-shaped flask, 1.05 mmol (1.34 g) of t-BuFpybIr, 10.5 mmol (1.81 g) of Fppy and 50 ml of glycerin were added. Heated to reflux for minutes. After allowing to cool, water was added, and the resulting precipitate was filtered with a centrifuge and washed with hexane to obtain metal complex compound 15 as an orange solid (1.29 g, yield 80%).
¹ H-NMR (CDCl ₃ -d): δ 10.07 (d, 1H, J = 6.3 Hz), 8.09 (s, 2H), 7.98-7.94 (m, 2H), 7.56 (dd, 1H, J = 8.6 , 5.7 Hz), 7.52-7.50 (m, 1H), 7.42 (d, 2H, J = 6.3 Hz), 6.84 (dd, 2H, J = 6.3, 2.3 Hz), 6.77 (t, 1H, JH-F = 11.7 Hz), 6.46 (td, 1H, J = 8.6, 2.9 Hz), 5.77 (dd, 1H, J = 9.7, 2.9 Hz), 1.28 (s, 18H)
ESI-MS m / z = 744.3010 (744.2180 required for [C35H32F3IrN3] +)

Synthesis Example 18 (Synthesis of metal complex compound 16)
According to the synthesis route shown in Synthesis Example 17, metal complex compound 15 was synthesized.
Then, 1.66 mmol (1.29 g) of metal complex compound 15, 16.6 mmol (1.08 g) of potassium cyanide and 100 ml of methanol were added to a 500 ml eggplant-shaped flask, and the mixture was heated to reflux for 3 days under a nitrogen stream. The product was collected by filtration and washed with hexane to give a yellow powder. Purification by silica gel column chromatography (developing solvent: methylene chloride) gave a yellow powder of metal complex compound 16 (0.46 g, yield 36%).
¹ H-NMR (CDCl ₃ -d): δ10.01 (d, 1H, J = 5.2 Hz), 8.10 (d, 2H, J = 1.7 Hz), 8.00-7.99 (m, 2H), 7.63 (dd, 1H, J = 8.6, 5.2 Hz), 7.49 (d, 2H, J = 6.3Hz), 7.46 (td, 1H, J = 5.6, 3.1 Hz), 6.82-6.80 (m, 3H), 6.51 (td, 1H , J = 8.7, 2.5 Hz), 5.76 (dd, 1H, J = 9.2, 2.3 Hz), 1.30 (s, 18H)
FT-IR (KBr): 2112.47cm ^-1 [ν (CN)]

The ultraviolet absorption spectrum of the metal complex compounds synthesized in the synthesis examples 1 to 13, 16 and 18 and the low temperature emission spectrum at room temperature and 77K are shown in FIGS. Table 2 shows the wavelengths of maximum light emission or typical absorption peaks.

In addition, X-ray crystal structure analysis diagrams of metal complex compounds 3, 4, 9, 29 and 15 are shown in FIGS. 46 to 55, and photophysical chemical data of the synthesized metal complex compounds (quantum yield, excitation lifetime, radiation and non-radiation). The rate constant) is shown in Table 3, and the redox potential by cyclic voltammetry is shown in Table 4.

Synthesis Example 19 (Optical resolution of metal complex compound 29)
The metal complex compound 29 obtained in Synthesis Example 11 was collected by HPLC. “CHIRALPAK (registered trademark) IA” (manufactured by Daicel Chemical Industries, Ltd.) was used as the column, and the developing solvent was dichloromethane (flow rate 0.5 ml / min). A chromatogram at a UV detection wavelength of 380 nm is shown in FIG. From FIG. 56, the Λ body and the Δ body were clearly separated and could be divided.
In addition, FIG. 57 shows circular dichroism (CD) spectra obtained by optical division. In FIG. 57, from the positive and negative of the Cotton effect around 270 nm, the broken-line complex is attributed to the Λ body and the solid line to the Δ body. Further, a circularly polarized light emission spectrum is shown in FIG.
In addition, FIG. 59 shows the X-ray structure of the racemate before dividing these structures. From FIG. 59, it was found that the metal complex compound 29 is a crystal in which the Λ-form and Δ-form structures are alternately stacked.

Synthesis Example 20 (Optical resolution of metal complex compound 30)
As in Synthesis Example 19, a chromatogram obtained by optical resolution of metal complex compound 30 is shown in FIG.
In addition, FIG. 61 shows circular dichroism (CD) spectra obtained by optical division. In FIG. 61, from the positive and negative of the Cotton effect around 270 nm, the broken-line complex is assigned as Λ and the solid line as Δ. Further, a circularly polarized light emission spectrum is shown in FIG.

Example 1
Using the metal complex compound 4, an organic EL device comprising a glass substrate / anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode was produced.
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. 4,4 ′, 4 ″ -tris (carbazol-9-yl) -triphenylamine (TCTA) used for the hole transport layer by vacuum deposition on the surface on which the ITO transparent electrode after cleaning is formed ) With a film thickness of 95 nm. Next, a mixture of the metal complex compound 4 and the compound (C-3) used in the light emitting layer (the mass ratio of the metal complex compound 4 and the compound (C-3) is 1.5: 20) is placed on the hole transport layer of the TCTA. A film was formed by vacuum evaporation to obtain a light emitting layer. The thickness of this light emitting layer was 30 nm. Subsequently, the above compound (B-20) having a thickness of 25 nm was formed, and subsequently, tris (8-hydroxyquinoline) aluminum (Alq ₃ ) having a thickness of 5 nm was formed by a vacuum evaporation method. Furthermore, a 1 nm-thick lithium fluoride film was formed by vacuum deposition to form an electron injection layer. Finally, an aluminum (Al) cathode having a film thickness of 150 nm was formed by a vacuum vapor deposition method to produce an organic EL element.
Using the obtained organic EL element, a DC voltage was applied with the Al electrode minus and the ITO transparent electrode plus. As a result, light emission of 111 cd / m ² was obtained at a voltage of 5 V and a current density of 0.6 mA / cm ² , the chromaticity coordinates were (0.29, 0.53), and the light emission efficiency was 18.6 cd / A. . The results are shown in Table 5. An EL spectrum is shown in FIG.

Example 2
In Example 1, the ratio of the mixture of the metal complex compound 4 and the compound (C-3) used in the light-emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-3) is 0.4: 20). Table 5 shows the results of producing an organic EL device in the same manner except that the change was made, and evaluating in the same manner. An EL spectrum is shown in FIG.
Example 3
In Example 1, the ratio of the mixture of the metal complex compound 4 and the compound (C-3) used for the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-3) is 0.8: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.
Example 4
In Example 1, the ratio of the mixture of the metal complex compound 4 and the compound (C-3) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-3) is 3.0: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.

Example 5
In Example 1, an organic EL device was prepared in the same manner except that the compound (C-7) was used instead of the compound (C-3) used in the light emitting layer, and the results of the evaluation were shown in Table 5. It was. An EL spectrum is shown in FIG.
Example 6
In Example 5, the ratio of the mixture of the metal complex compound 4 and the compound (C-7) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-7) is 0.8: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.
Example 7
In Example 5, the ratio of the mixture of the metal complex compound 4 and the compound (C-7) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-7) is 3.0: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.

Example 8
In Example 1, an organic EL device was prepared in the same manner except that the following BCP was used instead of the compound (C-1) and the compound (B-20) instead of the compound (C-3) used in the light emitting layer. The results of evaluation in the same manner are shown in Table 5. An EL spectrum is shown in FIG.

Example 9
In Example 8, the ratio of the mixture of the metal complex compound 4 and the compound (C-1) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-1) is 0.8: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.
Element Example 10
In Example 8, the ratio of the mixture of the metal complex compound 4 and the compound (C-1) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-1) is 3.0: 20). An organic EL device was produced in the same manner except that it was changed, and the results evaluated in the same manner are shown in Table 5. An EL spectrum is shown in FIG.

Example 11
In Example 1, an organic EL device was prepared in the same manner except that the compound (D-1) was used instead of the compound (C-3) used in the light emitting layer, and the results of the evaluation were shown in Table 5. It was. The EL spectrum is shown in FIG.
Example 12
In Example 1, an organic EL device was prepared in the same manner except that the compound (C-10) was used instead of the compound (C-3) used in the light emitting layer, and the results of the evaluation were shown in Table 5. It was. An EL spectrum is shown in FIG.

Example 13
Using the metal complex compound 4, an organic EL device comprising a glass substrate / anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode was produced.
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. On the surface where the ITO transparent electrode after cleaning is formed, the following compound (F-1) used for the hole injection layer by vacuum deposition is 85 nm, and TCTA used for the hole transport layer is 10 nm in thickness. A film was formed. Next, a mixture of the metal complex compound 4 and the compound (C-3) used in the light emitting layer (the mass ratio of the metal complex compound 4 and the compound (C-3) is 1.5: 20) is placed on the hole transport layer of the TCTA. A film was formed by vacuum evaporation to obtain a light emitting layer. The thickness of this light emitting layer was 30 nm. Subsequently, (B-20) with a film thickness of 25 nm and subsequently Alq ₃ with a film thickness of 5 nm were formed by a vacuum evaporation method. Furthermore, a 1 nm-thick lithium fluoride film was formed by vacuum deposition to form an electron injection layer. Finally, an Al cathode having a film thickness of 150 nm was formed by a vacuum vapor deposition method to produce an organic EL element.
Using the obtained organic EL element, a DC voltage was applied with the Al electrode minus and the ITO transparent electrode plus. As a result, light emission of 109 cd / m ² was obtained at a voltage of 7.8 V and a current density of 0.6 mA / cm ² , the chromaticity coordinates were (0.31, 0.52), and the light emission efficiency was 18.3 cd / A. there were. The results are shown in Table 5. An EL spectrum is shown in FIG.

Example 14
In Example 13, the ratio of the mixture of the metal complex compound 4 and the compound (C-3) used in the light-emitting layer was changed to (the mass ratio of the metal complex compound 4 and the compound (C-3) was 0.8: 20). Table 5 shows the results of producing an organic EL device in the same manner except that the change was made, and evaluating in the same manner. An EL spectrum is shown in FIG.
Example 15
In Example 13, the ratio of the mixture of the metal complex compound 4 and the compound (C-3) used in the light emitting layer is changed to (the mass ratio of the metal complex compound 4 and the compound (C-3) is 3.0: 20). Table 5 shows the results of producing an organic EL device in the same manner except that the change was made, and evaluating in the same manner. An EL spectrum is shown in FIG.
Example 16
In Example 13, an organic EL device was prepared in the same manner except that the compound (D-1) was used instead of the compound (C-3) used in the light emitting layer, and the results of evaluation were shown in Table 5. It was. An EL spectrum is shown in FIG.

Example 17
Using the metal complex compound 4, an organic EL device comprising a glass substrate / anode / hole transport layer / light emitting layer 1 / light emitting layer 2 / hole blocking layer / electron transport layer / electron injection layer / cathode was produced.
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. On the surface on the side where the ITO transparent electrode after the cleaning was formed, TCTA used for the hole transport layer was formed in a film thickness of 85 nm by a vacuum deposition method. Next, the mixture of (F-2) and (C-3) (the mass ratio of (F-2) and (C-3) used in the light-emitting layer 1 is 0.4: 20) is the hole transport layer of TCTA. A light emitting layer 1 was obtained by forming a film thereon by a vacuum deposition method. The thickness of the light emitting layer 1 was 5 nm. Further, a mixture of the metal complex compound 4 and (C-3) used for the light emitting layer 2 (the mass ratio of the metal complex compound 4 and (C-3) is 0.4: 20) is formed on the light emitting layer 1 to a thickness of 30 nm. As a result, the light emitting layer 2 was obtained. Subsequently, (B-20) with a film thickness of 25 nm and subsequently Alq ₃ with a film thickness of 5 nm were formed by a vacuum evaporation method. Furthermore, a 1 nm-thick lithium fluoride film was formed by vacuum deposition to form an electron injection layer. Finally, an Al cathode having a film thickness of 150 nm was formed by a vacuum vapor deposition method to produce an organic EL element.
Using the obtained organic EL element, a DC voltage was applied with the Al electrode minus and the ITO transparent electrode plus. As a result, light emission of 97 cd / m ² was obtained at a voltage of 8.7 V and a current density of 1.7 mA / cm ² , the chromaticity coordinates were (0.35, 0.46), and the light emission efficiency was 5.7 cd / A. there were. From this, it was confirmed that the light emission was white. The results are shown in Table 5. An EL spectrum is shown in FIG.

Example 18
In Example 17, a higher voltage was applied. As a result, emission of 3921 cd / m ² was obtained at a voltage of 13.9 V and a current density of 100 mA / cm ² , the chromaticity coordinates were (0.32: 0.42), and the luminous efficiency was 3.9 cd / A. . From this, it was confirmed that the light emission was white. The results are shown in Table 5. An EL spectrum is shown in FIG.

Example 19
In Example 1, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 20
In Example 2, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 21
In Example 3, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 22
In Example 4, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 23
In Example 5, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 24
In Example 6, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 25
In Example 7, showing the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 26
In Example 8, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 27
In Example 9, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 28
In Example 10, the device performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , 10 mA / cm ² is shown in Table 6.

Example 29
In Example 11, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 30
In Example 12, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 31
In Example 13, the device performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , 10 mA / cm ² is shown in Table 6.

Example 32
In Example 14, the device performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , 10 mA / cm ² is shown in Table 6.

Example 33
In Example 15, it shows the device performance in the case where the current density 0.1 mA / cm ^2, and 1.0 mA / cm ^2, 10 mA / cm ² in Table 6.

Example 34
In Example 16, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 6.

Example 35
In Example 1, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 10, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 36
In Example 35, the element performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² is shown in Table 8.

Example 37
In Example 13, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 10, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 38
In Example 37, the element performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² is shown in Table 8.

Example 39
In Example 1, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 40
In Example 39, the device performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² is shown in Table 8.

Example 41
In Example 3, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 42
In Example 41, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 43
In Example 4, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured in the same manner. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 44
In Example 43, the element performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² is shown in Table 8.

Example 45
In Example 13, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 46
In Example 45, Table 8 shows element performances when the current density was 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² .

Example 47
In Example 15, an organic EL device was produced in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 48
In Example 47, Table 8 shows element performances when the current density was 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² .

Example 49
An organic EL device was prepared in the same manner as in Example 1 except that the complex used for the light emitting layer was changed to the metal complex compound 38, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 50
In Example 49, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 51
In Example 13, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 52
In Example 51, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 53
In Example 14, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 54
Table 8 shows the element performance in Example 53 when the current density was 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² .

Example 55
In Example 1, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 56
In Example 55, Table 8 shows element performances when the current density was 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² .

Example 57
In Example 4, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 58
In Example 57, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 59
In Example 5, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 60
In Example 59, the element performance when the current density is 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² is shown in Table 8.

Example 61
In Example 6, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 62
In Example 61, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 63
In Example 7, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 16, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. An EL spectrum is shown in FIG.

Example 64
In Example 63, it shows the device performance in the case where the current density 0.1 mA / cm ^2, a ^{1.0mA / cm 2, 10mA / cm} 2 in Table 8.

Example 65
In Example 7, an organic EL device was prepared in the same manner except that the complex used for the light emitting layer was changed to the metal complex compound 24, and the voltage, current density, luminance, chromaticity coordinates, and luminous efficiency were measured. The results are shown in Table 7. The EL spectrum is shown in FIG.

Example 66
In Example 65, Table 8 shows element performances when the current density was 0.1 mA / cm ² , 1.0 mA / cm ² , and 10 mA / cm ² .

  From Tables 6-8, the organic EL element which used the metal complex compound of this invention for the light emitting layer has chromaticity coordinates (0.42 or less, 0.59 or less), and is excellent (0.2 or less). 0.5 or less), and more excellent (0.2 or less, 0.4 or less). Since many of the chromaticity coordinates are (0.2 or less, 0.5 or less), it can be seen that light emission in a blue region with high color purity can be obtained. It can also be seen that high luminance and high luminous efficiency can be obtained at a low voltage.

  As described above in detail, the organic EL device using the metal complex compound of the present invention has high luminous efficiency, emits blue light with high color purity with short wavelength light emission, and is combined with other light emitting compounds. White light emission is also possible. For this reason, it can be applied to the fields of various display elements, displays, backlights, illumination light sources, signs, signboards, interiors, etc., and is suitable as a display element for color displays, and particularly suitable for materials for organic EL elements.

3 is a diagram showing a UV absorption spectrum of metal complex compound 3. FIG. 4 is a diagram showing a UV absorption spectrum of metal complex compound 4. FIG. FIG. 4 is a diagram showing a UV absorption spectrum of metal complex compound 5. 4 is a diagram showing a UV absorption spectrum of a metal complex compound 6. FIG. It is a figure which shows the UV absorption spectrum of the metal complex compound 7. 3 is a diagram showing a UV absorption spectrum of a metal complex compound 8. FIG. It is a figure which shows the UV absorption spectrum of the metal complex compound 9. 2 is a diagram showing a UV absorption spectrum of the metal complex compound 10. FIG. 2 is a diagram showing a UV absorption spectrum of a metal complex compound 11. FIG. It is a figure which shows the UV absorption spectrum of the metal complex compound 12. It is a figure which shows the UV absorption spectrum of the metal complex compound 29. 2 is a diagram showing a UV absorption spectrum of a metal complex compound 30. FIG. 4 is a diagram showing a UV absorption spectrum of a metal complex compound 24. FIG. 4 is a diagram showing a UV absorption spectrum of a metal complex compound 38. FIG. 2 is a diagram showing a UV absorption spectrum of a metal complex compound 16. FIG. 4 is a diagram showing a room temperature emission spectrum of the metal complex compound 3. FIG. It is a figure which shows the room temperature emission spectrum of the metal complex compound 4. It is a figure which shows the room temperature emission spectrum of the metal complex compound 5. It is a figure which shows the room temperature emission spectrum of the metal complex compound 6. It is a figure which shows the room temperature emission spectrum of the metal complex compound 7. It is a figure which shows the room temperature emission spectrum of the metal complex compound 8. It is a figure which shows the room temperature emission spectrum of the metal complex compound 9. 1 is a diagram showing a room temperature emission spectrum of a metal complex compound 10. FIG. It is a figure which shows the low temperature emission spectrum of the metal complex compound 11. It is a figure which shows the room temperature emission spectrum of the metal complex compound 12. It is a figure which shows the room temperature emission spectrum of the metal complex compound 29. FIG. 2 is a diagram showing a room temperature emission spectrum of a metal complex compound 30. FIG. 3 is a diagram showing a room temperature emission spectrum of a metal complex compound 24. FIG. 3 is a diagram showing a room temperature emission spectrum of a metal complex compound 38. FIG. 2 is a diagram showing a room temperature emission spectrum of the metal complex compound 16. FIG. 3 is a diagram showing a low temperature emission spectrum of a metal complex compound 3. FIG. 4 is a diagram showing a low temperature emission spectrum of a metal complex compound 4. FIG. 4 is a diagram showing a low temperature emission spectrum of a metal complex compound 5. FIG. 4 is a diagram showing a low temperature emission spectrum of a metal complex compound 6. FIG. It is a figure which shows the low temperature emission spectrum of the metal complex compound 7. 4 is a diagram showing a low temperature emission spectrum of a metal complex compound 8. FIG. It is a figure which shows the low temperature emission spectrum of the metal complex compound 9. 1 is a diagram showing a low temperature emission spectrum of a metal complex compound 10. FIG. It is a figure which shows the low temperature emission spectrum of the metal complex compound 11. It is a figure which shows the low temperature emission spectrum of the metal complex compound 12. It is a figure which shows the low temperature emission spectrum of the metal complex compound 29. 4 is a diagram showing a low temperature emission spectrum of the metal complex compound 30. FIG. 3 is a diagram showing a low temperature emission spectrum of a metal complex compound 24. FIG. 3 is a diagram showing a low temperature emission spectrum of a metal complex compound 38. FIG. 4 is a diagram showing a low temperature emission spectrum of the metal complex compound 16. FIG. It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 3 (1 molecule). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 3 (2 molecules). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 3 (2 molecules). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 4 (1 molecule). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 4 (2 molecules). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 4 (2 molecules). 3 is a diagram showing an X-ray crystal structure analysis of a metal complex compound 9. FIG. 3 is a diagram showing an X-ray crystal structure analysis of a metal complex compound 29. FIG. It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 15 (2 molecules). It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 15 (2 molecules). It is a figure which shows the chromatogram in UV detection wavelength 380nm in HPLC of the metal complex compound 29. FIG. It is a figure which shows the circular dichroism (CD) spectrum of the metal complex compound 29 optically divided. It is a figure which shows the circularly polarized light emission spectrum of the metal complex compound 29. FIG. It is a figure which shows the X-ray crystal structure analysis of the metal complex compound 29 (racemic body). It is a figure which shows the chromatogram in UV detection wavelength 380nm in HPLC of the metal complex compound 30. It is a figure which shows the circular dichroism (CD) spectrum of the metal complex compound 30 optically divided. 3 is a diagram showing a circularly polarized light emission spectrum of a metal complex compound 30. FIG. It is a figure which shows the EL spectrum in the organic EL element of Examples 1-4. It is a figure which shows the EL spectrum in the organic EL element of Examples 5-7. It is a figure which shows the EL spectrum in the organic EL element of Examples 8-10. FIG. 12 is a diagram showing an EL spectrum in the organic EL element of Example 11. It is a figure which shows the EL spectrum in the organic EL element of Example 12. It is a figure which shows the EL spectrum in the organic EL element of Examples 13-15. It is a figure which shows the EL spectrum in the organic EL element of Example 16. It is a figure which shows the EL spectrum in the organic EL element of Examples 17-18. It is a figure which shows the EL spectrum in the organic EL element of Example 35. 6 is a diagram showing an EL spectrum in an organic EL element of Example 37. FIG. It is a figure which shows the EL spectrum in the organic EL element of Example 39. 6 is a diagram showing an EL spectrum in an organic EL element of Example 41. FIG. It is a figure which shows the EL spectrum in the organic EL element of Example 43. It is a figure which shows the EL spectrum in the organic EL element of Example 45. It is a figure which shows the EL spectrum in the organic EL element of Example 47. It is a figure which shows the EL spectrum in the organic EL element of Example 49. FIG. 4 is a diagram showing an EL spectrum in the organic EL element of Example 51. 6 is a diagram showing an EL spectrum in an organic EL device of Example 53. FIG. It is a figure which shows the EL spectrum in the organic EL element of Example 55. FIG. 10 is a diagram showing an EL spectrum in the organic EL element of Example 57. It is a figure which shows the EL spectrum in the organic EL element of Example 59. 6 is a diagram showing an EL spectrum in an organic EL device of Example 61. FIG. FIG. 10 is a diagram showing an EL spectrum in an organic EL element of Example 63. It is a figure which shows the EL spectrum in the organic EL element of Example 65.

Claims (15)

A metal complex compound having a structure represented by the following general formula (I) having a bidentate chelate ligand and a tridentate chelate ligand.

(In the formula, ring A is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
Ring B is an optionally substituted heterocyclic group having 2 to 20 carbon atoms, N is a nitrogen atom, Y is a carbon atom or a nitrogen atom,
L and Z are each independently an organic group containing any atom of Groups 14-16 of the Periodic Table;
X is a monovalent ligand containing any atom of Groups 14-17 of the Periodic Table;
R is a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkylamino group having 1 to 12 carbon atoms, C6-C20 arylamino group which may have a substituent, C1-C12 alkoxy group which may have a substituent, C1-C12 halogen which may have a substituent An alkoxy group, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, and a substituent. It has a C2-C20 heterocyclic group, a C1-C12 halogenated alkyl group which may have a substituent, a C2-C12 alkenyl group which may have a substituent, and a substituent. An alkynyl group having 2 to 12 carbon atoms, or 3 to 20 carbon atoms which may have a substituent A cycloalkyl group. n is an integer of 0 to 4, and when n is 2 or more, each R may be the same or different, and adjacent ones may be bonded to each other to form a cyclic structure.
However, the tridentate chelate ligand and / or the bidentate chelate ligand contains an electron-withdrawing group. ) In the general formula (I), X represents a cyano group, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, a hydrogen atom, Si (R ′) ₃ (R ′ represents the same group as the above R), or a substitution. The metal complex compound according to claim 1, which is a phenyl group.   The metal complex compound according to claim 1, wherein in the general formula (I), both the tridentate chelate ligand and the bidentate chelate ligand contain an electron-withdrawing group.   The metal complex compound according to claim 1, wherein in the general formula (I), the electron-withdrawing group is a halogen atom, a cyano group, a nitro group, a halogen atom-containing alkyl group, an ester group, or an aldehyde group. The metal complex compound according to claim 1, wherein in the general formula (I), the tridentate chelate ligand is a compound represented by the following general formula (1) or (2).

(In the formula, rings B, Y and R are the same as described above.) 2. The metal complex compound according to claim 1, wherein in the general formula (I), the tridentate chelate ligand is a compound represented by any one of the following general formulas (3) to (16).

(In formula, R < ¹ > -R < ²³ > is respectively the same as said R, and adjacent ones among R < ¹ > -R < ²³ > may combine with each other to form a cyclic structure.) The metal complex according to claim 1, wherein in the general formula (I), the bidentate chelate ligand formed by LZ is a compound represented by any one of the following general formulas (17) to (22). Compound.

(Wherein R ^{24 to} R ⁴⁵ are the same as R, respectively, and adjacent ones of R ^{24 to} R ⁴⁵ may be bonded to each other to form a cyclic structure.) The metal complex compound according to claim 1, which is represented by any one of the following general formulas (I-1) to (I-12).

(Wherein R ^{46 to} R ⁵⁸ are the same as R. l and l ′ are integers of 0 to 2, m and m ′ are integers of 0 to 3, and n, n ′, n ″ and n ′ ″ are integers of 0 to 4. When l, l ′, m, m ′, n, n ′, n ″, or n ′ ″ is 2 or more, R ⁴⁶ to Two or more of R ⁵⁸ may be the same or different, and adjacent ones may be bonded to each other to form a cyclic structure.) The metal complex compound according to claim 1, which is represented by any one of the following general formulas (I-13) to (I-24).

Wherein R ⁴⁶ and R ^{48 to} R ⁵⁹ are the same as R. l, l ′ and l ″ are integers from 0 to 2, and m and m ′ are integers from 0 to 3. N, n ′, n ″ and n ′ ″ are integers from 0 to 4. l, l ′, l ″, m, m ′, n, n ′, n ″ or n ″. When 'is 2 or more, two or more of R ⁴⁶ and R ^{48 to} R ⁵⁹ may be the same or different, and adjacent ones are bonded to each other to form a cyclic structure. May be.)   The material for organic electroluminescent elements which consists of a metal complex compound of Claim 1.   In the organic electroluminescent element in which an organic thin film layer composed of at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes, at least one layer of the organic thin film layer comprises the metal complex compound according to claim 1. An organic electroluminescence element that contains and emits light when a voltage is applied between both electrodes.   The organic electroluminescence device according to claim 11, wherein the emission color is white.   The organic electroluminescent element according to claim 11 or 12, wherein the light emitting layer contains the metal complex compound.   The organic electroluminescence device according to claim 13, wherein the light emitting layer contains a light emitting dopant.   The organic electroluminescence device according to claim 11 or 12, wherein the layer containing the metal complex compound is formed by coating.

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