WO2012066686A1 - Complexe de métal de transition et son utilisation - Google Patents

Complexe de métal de transition et son utilisation Download PDF

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WO2012066686A1
WO2012066686A1 PCT/JP2010/070749 JP2010070749W WO2012066686A1 WO 2012066686 A1 WO2012066686 A1 WO 2012066686A1 JP 2010070749 W JP2010070749 W JP 2010070749W WO 2012066686 A1 WO2012066686 A1 WO 2012066686A1
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transition metal
metal complex
general formula
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青木　伸
洋介 久松
紘喜 大和田
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学校法人東京理科大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a transition metal complex and its use.
  • organic EL elements organic electroluminescence elements
  • Reduction of power consumption and extension of the life of the device are listed as indispensable issues in order to be handled equally with displays such as liquid crystal display devices and light emitting diodes that are already known in the world.
  • the cyclometallate type iridium (III) complex has excellent light emission characteristics and is widely used as an organic EL element material.
  • a cyclometalate type iridium (III) complex having an amino group or a carboxy group has been disclosed (for example, see WO08 / 059910).
  • the blue phosphorescent device has problems such as low external quantum efficiency and insufficient color purity.
  • Various excellent blue light-emitting materials and host materials have been developed for these problems.
  • Japanese Patent Application Laid-Open No. 2010-195708 discloses a compound having a carbazolyl group, which has advantages such as high light emission efficiency, color purity, and long life, and is suitable as a light emitting material for an organic EL element that emits blue light.
  • Japanese Patent Laid-Open No. 2010-24149 discloses a seven-membered ring structure such as a 10,11-dihydrobenzocycloheptene derivative suitable as a light-emitting material for an organic EL device having excellent characteristics such as low voltage driving and high color purity. Discloses compounds having:
  • An object of the present invention is to provide a compound capable of emitting blue light with high emission quantum efficiency, a phosphorescent material and an organic EL device using the compound.
  • a transition metal complex comprising a Group 8 to Group 10 transition metal and a ligand represented by the following general formula (1) coordinated to the transition metal.
  • R 1 and R 2 each independently represent a substituent.
  • m and n each independently represents an integer of 0 to 4.
  • Z represents a functional group having a Hammett's substituent constant ( ⁇ p ) of 0 to 0.8.
  • Z is a haloalkyl group, cyano group, thiocyanato group, sulfo group, alkyl or arylsulfonyl group, sulfonamido group, sulfino group, sulfamyl group, formyl group, acyl group,
  • R 1 is a hydrogen atom or an alkyl group
  • n is 0.
  • a phosphorescent material comprising the transition metal complex according to any one of [1] to [3].
  • An organic electroluminescence device comprising:
  • the transition metal complex of the present invention is a transition metal complex containing a group 8 to group 10 transition metal and a ligand represented by the following general formula (1) coordinated to the transition metal.
  • R 1 and R 2 each independently represent a substituent.
  • m and n each independently represents an integer of 0 to 4.
  • Z represents a functional group having a Hammett's substituent constant ( ⁇ p ) of 0 to 0.8.
  • # Represents the coordinate bond position with the transition metal.
  • the present invention is based on the discovery that the transition metal complex represented by the general formula (1) emits light with high emission quantum efficiency and exhibits an emission peak in a blue region of 420 nm or more and less than 500 nm. Therefore, according to the present invention, it is possible to provide a transition metal complex capable of emitting light in a blue wavelength region with high emission quantum efficiency, and a use using the transition metal complex, for example, a phosphorescent material and an organic EL element. it can.
  • process is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The present invention is described in detail below.
  • the transition metal complex of the present invention is a transition metal complex having a group 8 to group 10 transition metal and a ligand represented by the above general formula (1) coordinated to the transition metal.
  • R 1 and R 2 each independently represent a substituent.
  • R 1 and R 2 examples include an alkyl group, alkenyl group, aromatic, alkoxy group, halogen atom, haloalkyl group, alkyl or arylcarbonyl group, cyano group, thiocyanato group, sulfo group, alkyl or arylsulfonyl Groups, sulfonamido groups, sulfino groups, sulfamyl groups, formyl groups, acyl groups, carbamoyl groups, nitroso groups, azide groups, or alkylarylazio groups.
  • the substituent may further have a substituent if possible.
  • R 1 is not particularly limited, but is preferably ortho to the position of Z from the viewpoint of synthesis efficiency and electronic effect.
  • n and n each independently represents an integer of 0 to 4.
  • m and n are each 2 or more, the corresponding R 1 and R 2 may be the same or different, and there are no particular restrictions on the relative positions.
  • R 1 is preferably an alkyl group, a halogen atom, a haloalkyl group, or an aromatic group, more preferably a halogen atom or an alkyl group, from the viewpoints of emission quantum efficiency and emission wavelength.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the aromatic group is preferably an aromatic group having 3 to 24 carbon atoms, more preferably an aromatic group having 4 to 20 carbon atoms.
  • R 2 is preferably a halogen atom, an alkyl group, or an aromatic group from the viewpoint of light emission quantum efficiency and light emission wavelength.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the aromatic group is preferably an aromatic group having 3 to 24 carbon atoms, more preferably an aromatic group having 4 to 20 carbon atoms.
  • m is preferably an integer of 0 to 2, more preferably 0 or 1, from the viewpoints of emission quantum efficiency and emission wavelength.
  • n is preferably an integer of 0 to 2, and more preferably 0, from the viewpoints of emission quantum efficiency and emission wavelength.
  • Z in the general formula (1) represents a functional group having a Hammett's substituent constant ( ⁇ p ) of 0 to 0.8. If the Hammett's substituent constant is outside this range, the emission wavelength shifts to the longer wavelength side and blue emission cannot be expected.
  • ⁇ p a standard substituent constant that is usually used for electron withdrawing groups is applied. “ ⁇ ” is defined based on the acid dissociation constant (K a ) of substituted benzoic acid at 25 ° C. in water.
  • the functional group represented by Z is preferably a functional group having a Hammett's substituent constant of 0.3 to 0.7 from the viewpoints of light emission quantum efficiency and light emission wavelength.
  • Examples of the functional group represented by Z include a haloalkyl group, a cyano group, a thiocyanato group, a sulfo group, an alkyl or arylsulfonyl group, a sulfonamide group, a sulfino group, a sulfamyl group, a formyl group, an acyl group, a carbamoyl group, and a nitroso group. , An azide group, or an alkyl or aryl diazo group.
  • the acyl group may be substituted with a halogen atom.
  • the alkylsulfonyl group represented by Z may be substituted with a halogen.
  • the halogen atom represented by Z is preferably a fluorine atom from the viewpoint of emission quantum efficiency and emission wavelength.
  • the halogen atom in the haloalkyl group represented by Z is preferably a fluorine atom from the viewpoint of emission quantum efficiency and emission wavelength.
  • the acyl group represented by Z is not particularly limited as long as it satisfies the above-described substituent constant, and examples thereof include an acyl group having 2 to 20 carbon atoms, and further has a substituent such as a halogen atom. It may be.
  • the acyl group represented by Z is preferably an acyl group having 2 to 20 carbon atoms, more preferably an acyl group having 2 to 12 carbon atoms, More preferred is an acyl group of 2 to 4.
  • the alkyl group in the functional group represented by Z is preferably an alkyl group having 1 to 20 carbon atoms, and is an alkyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and the aryl group in the functional group represented by Z is preferably an aryl group having 6 to 24 carbon atoms, More preferred is an aryl group having 6 to 20 carbon atoms.
  • the functional group represented by Z is particularly preferably an acyl group, a cyano group, a thiocyanato group, a sulfo group, a sulfoamide group, or a formyl group from the viewpoint of light emission quantum efficiency.
  • Examples of the group 8 to group 10 transition metal in the transition metal complex according to the present invention include ruthenium, rhodium, palladium, osmium, platinum and iridium. Among these, iridium, ruthenium, or platinum is preferable from the viewpoint of light emission quantum efficiency, and iridium is more preferable.
  • the transition metal complex according to the present invention is a complex compound containing a group 8 to group 10 transition metal as a central metal, and has at least one ligand represented by the general formula (1).
  • the total number of ligands in the transition metal complex of the present invention is appropriately selected according to the central metal.
  • the coordination number in the transition metal complex is generally 6, and the ligand represented by the ligand represented by the general formula (1) is bidentate, respectively. It is a ligand. Therefore, the transition metal complex in the present invention can have other ligands other than the ligand represented by the general formula (1) in addition to the ligand represented by the general formula (1). . For example, dimming can be adjusted by appropriately selecting other ligands. Although it does not specifically limit as another ligand, From a viewpoint of the light emission quantum efficiency and the manufacture aptitude of a fluorescent compound, it is preferable that it is a ligand which has an arylpyridine structure.
  • the transition metal complex in the present invention is preferably a compound represented by the following general formula (1a).
  • i represents an integer of 1 to 3
  • R 1 to R 2 , Z, m and n are the same as R 1 to R 2 , Z, m and n in the general formula (1), respectively. It is.
  • the plurality of R 1 to R 2 or Z may be the same or different.
  • the number of ligands represented by the general formula (1) may be 1 or more, and from the viewpoint of light emission quantum efficiency, the number of ligands represented by the general formula (1) is 2 or 3 is preferable, and 3 is more preferable. That is, the transition metal complex in the present invention is preferably represented by the following general formula (1b).
  • Z, m and n are, R 1 ⁇ R 2, Z , respectively m and n are the same in the general formula (1).
  • transition metal complex in the present invention is not limited thereto.
  • the transition metal complex according to the present invention is not particularly limited and can be appropriately selected from conventionally known methods.
  • a functional group having Hammett's substituent constant in the above range can be introduced regioselectively by reacting with an electrophile.
  • the transition metal complex which has a desired light emission wavelength can be manufactured by converting the introduce
  • a compound represented by the following general formula (3) is obtained by formylating a compound represented by the following general formula (2). And includes other steps as necessary.
  • a method for producing a compound represented by the following general formula (5) includes a step of formylating a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (3). And a step of converting a formyl group of the compound represented by the following general formula (3) into a cyano group, and includes other steps as necessary.
  • R 1, R 2, m and n are R 1, R 2 in the formula (1), m and Each is synonymous with n, and the preferred embodiments are also the same.
  • a commonly used formylating agent of an aromatic compound can be used without particular limitation.
  • Specific examples include Vilsmeier reagent and formyl fluoride.
  • the reaction conditions are not particularly limited as long as the target compound is obtained.
  • the reaction conditions described in US Patent Application Publication No. 2005/0253135 can be used.
  • the step of obtaining the compound represented by the above general formula (3) obtained by formylating the compound represented by the general formula (3) in the present invention further comprises a post-treatment step, a purification step, etc., as necessary. Further, it may be included. Thereby, the compound of General formula (3) as a transition metal complex concerning this invention is obtained.
  • a commonly used method can be used without particular limitation.
  • the formyl group is reacted with hydroxylamine.
  • a method of performing a dehydration reaction after hydroxyiminization can be used.
  • the conditions for the dehydration reaction are not particularly limited, and examples thereof include a method using an acid anhydride or acid halide as a dehydrating agent. The reaction conditions for this reaction can be appropriately selected according to the method used.
  • the transition metal complex in which Z in the general formula (1) is a carbamoyl group can be obtained, for example, by oxidizing the formyl body obtained above to a carboxy body and then amidating it.
  • the method for oxidizing the formyl group is not particularly limited, and can be appropriately selected from commonly used oxidation reactions.
  • the method for amidating the carboxy group is not particularly limited, and can be appropriately selected from commonly used reactions.
  • the transition metal complex in which Z in the general formula (1) is a thiocyanate group, a sulfo group, an acyl group, an alkyl group, or an arylsulfonyl group is, for example, a bisthiocyanate, a halosulfonic acid, It can be produced in the same manner as described above by using an acyl halide, alkyl, arylsulfonyl halide or the like.
  • the transition metal complex in which Z in the general formula (1) is a nitroso group or a diazo group is obtained by, for example, obtaining a nitro form using a nitrating agent instead of the formylating agent, Each can be manufactured by conversion.
  • Each of the above steps preferably further includes a purification step for purifying the obtained compound.
  • a purification step a commonly used method can be used without particular limitation. Examples thereof include a purification method using an ion exchange column or silica gel column chromatography, and a purification method including a step of sublimation or recrystallization.
  • the transition metal complex according to the present invention can be used for various applications.
  • functions such as sensitization effect, heat generation effect, color development effect, color fading effect, phosphorescence effect, phase change effect, photoelectric conversion effect, photomagnetic effect, photocatalytic effect, photocatalytic effect, light modulation effect, optical recording effect, radical generation effect, etc. It can also be used as a material, or conversely, a material having a light emitting function due to these effects.
  • the transition metal complex according to the present invention is particularly preferably used as an organic EL element material (organic EL material) from the viewpoint of the emission wavelength and the emission quantum efficiency.
  • the phosphorescent material according to the present invention is represented by the above-described transition metal complex according to the present invention, that is, the above-described general formula (1) that is coordinated to the transition metal of Group 8 to Group 10 and the transition metal.
  • a transition metal complex having a ligand is represented by the above-described transition metal complex according to the present invention, that is, the above-described general formula (1) that is coordinated to the transition metal of Group 8 to Group 10 and the transition metal.
  • a transition metal complex having a ligand having a ligand.
  • the phosphorescent material according to the present invention is preferably used as a blue phosphorescent material because it emits light with high emission quantum efficiency and exhibits an emission peak in a blue region of 420 nm or more and less than 500 nm.
  • the transition metal complex in the phosphorescent material the matters described in the present specification are applied as they are as the transition metal complex according to the present invention, and preferred embodiments are also the same.
  • the phosphorescent light-emitting material according to the present invention is particularly preferably an organic EL element material (organic EL material, organic EL material) from the viewpoints of emission wavelength and light emission quantum efficiency among the exemplary uses described above with respect to the transition metal complex. Used for.
  • the organic EL device includes a pair of electrodes, and at least one organic layer including a layer that is disposed between the electrodes and includes a phosphorescent material made of the transition metal complex according to the present invention described above. And an organic EL element.
  • the transition metal complex according to the present invention is a phosphorescent material capable of emitting light in the blue wavelength region with high emission quantum efficiency, a light emitting layer is formed by including the transition metal complex in an organic layer. Thus, a blue organic EL element with high luminous efficiency can be obtained.
  • the phosphorescent material according to the present invention may be contained in at least one of the organic layers.
  • the organic EL element is composed of an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode.
  • the single layer type organic EL element is an element composed of only a light emitting layer between an anode and a cathode.
  • the multilayer organic EL element facilitates injection of holes and electrons into the light emitting layer in addition to the light emitting layer, and facilitates recombination of holes and electrons in the light emitting layer.
  • it refers to a layer in which a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like are laminated.
  • typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode.
  • Anode / hole injection layer / light emitting layer / electron injection layer / cathode (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) An element structure in which a multilayer structure of anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode, etc., is considered.
  • the materials used for the hole transport layer, hole injection layer, light emitting layer, electron injection layer, and hole blocking layer are not particularly limited, and can be appropriately selected from known materials and used. Either a molecular system or a polymer system may be used.
  • a hole injection material that exhibits an excellent hole injection effect with respect to the light emitting layer and that can form a hole injection layer excellent in adhesion to the anode interface and thin film formation is used.
  • the materials used for each are called a hole injection material and a hole transport material.
  • the hole injecting material and the hole transporting material that can be used for the organic EL device material of the present invention are not particularly limited, and those conventionally used as a charge transporting material for holes in a photoconductive material, Any of known materials used for the hole injection layer of the organic EL device can be selected and used.
  • hole injection materials and hole transport materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, and arylamine derivatives. And amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilanes, aniline copolymers, and the like.
  • hole injecting material and the hole transporting material those described above can be used, but porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds can also be used.
  • porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds can also be used.
  • 4,4 ′, 4 ′′ -tris N- (3-methylphenyl) -N-phenyl, in which three triphenylamine units described in JP-A-4-308688 are linked in a starburst type. Amino) triphenylamine, etc.
  • examples of the hole injection material include phthalocyanine derivatives such as copper phthalocyanine and hydrogen phthalocyanine, and other aromatic dimethylidene compounds, p-type Si, p-type SiC, etc. These inorganic compounds can also be used as hole injection materials and hole transport materials.
  • an electron injection material that exhibits an excellent electron injection effect with respect to the light emitting layer and that can form an electron injection layer excellent in adhesion to the cathode interface and thin film formability is used.
  • electron injection materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, perylenetetracarboxylic acid derivatives, fluorenylidenemethane. Derivatives, anthrone derivatives, silole derivatives, triarylphosphine oxide derivatives, calcium acetylacetonate, sodium acetate and the like.
  • Preferred examples of the electron injecting material include metal complex compounds, nitrogen-containing five-membered ring derivatives, silole derivatives, and triarylphosphine oxide derivatives.
  • a metal complex compound usable in the present invention a metal complex of 8-hydroxyquinoline or a derivative thereof is suitable.
  • hole blocking material that can prevent a hole from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer.
  • hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolate) aluminum, and bis (2-methyl-8-hydroxyquinolinate) ( Gallium complex compounds such as 4-phenylphenolate) gallium and nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).
  • the transition metal complex according to the present invention is suitably used as a light-emitting layer, and constitutes an organic EL element together with other layers to obtain blue light emission.
  • the light emitting layer may contain other light emitting materials in addition to the transition metal complex according to the present invention.
  • known compounds such as fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, and styrylbenzene compounds may be used.
  • the other phosphorescence-emitting material different from the transition metal complex concerning this invention mentioned above can also be used.
  • Other phosphorescent light emitting materials here include 2-phenylpyridine and 2- (2′-benzothienyl) pyridine as ligands, transition metals and complexes such as iridium and platinum, porphyrin or tetraazaporphyrin Examples of the center metal include platinum.
  • Each of the above layers is formed by a dry method such as a vacuum deposition method or a sputtering method, an inkjet method, a casting method, a dip coating method, a bar coating method, a blade coating method, a roll coating method, a gravure coating method, a flexographic printing method, or a spray coating. It can carry out by wet methods, such as a method.
  • the film is formed by vacuum deposition.
  • the film thickness of each layer is appropriately determined according to the situation in consideration of the adaptability between the layers and the required total layer thickness, and is usually preferably in the range of 5 nm to 5 ⁇ m. .
  • the electrode of the organic EL device according to the present invention is preferably one in which a transparent conductive thin film is formed on a transparent substrate.
  • the substrate serves as a support for the organic electroluminescence element, and when the substrate side is a light emitting surface, it is preferable to use a transparent substrate having translucency in visible light.
  • the light transmittance is preferably 80% or more, and preferably 85% or more. More preferably, it is 90% or more.
  • glass substrates such as optical glass such as BK7, BaK1, and F2, quartz glass, alkali-free glass, borosilicate glass, and aluminosilicate glass, acrylic resin such as PMMA, polycarbonate, polyether sulfonate, polystyrene Polymer substrates such as polyolefins, epoxy resins, polyesters such as polyethylene terephthalate are used.
  • the thickness of the substrate is usually about 0.1 mm to 10 mm, but preferably 0.3 mm to 5 mm in view of mechanical strength, weight, etc., and 0.5 mm to 2 mm. More preferably.
  • the anode is usually formed on the substrate.
  • the anode is composed of a metal, alloy, conductive compound or the like having a high work function (4 eV or more), and is preferably formed as a transparent electrode on the transparent substrate.
  • metal oxides such as indium tin oxide (ITO), indium zinc oxide, and zinc oxide are generally used.
  • ITO is preferably used from the viewpoint of transparency and conductivity.
  • the film thickness of the transparent electrode is preferably 80 nm to 400 nm, and more preferably 100 nm to 200 nm, in order to ensure transparency and conductivity.
  • the anode is usually formed by a sputtering method, a vacuum deposition method or the like, and is preferably formed as a transparent conductive thin film.
  • the cathode facing the anode is composed of a metal, an alloy, or a conductive compound having a small work function (4 eV or less).
  • a metal an alloy, or a conductive compound having a small work function (4 eV or less).
  • a metal an alloy, or a conductive compound having a small work function (4 eV or less).
  • a metal an alloy, or a conductive compound having a small work function (4 eV or less.
  • aluminum, an aluminum-lithium alloy, a magnesium-silver alloy, lithium fluoride, and the like can be given.
  • a single layer may be used, or a multilayer may be formed by combining materials having different work functions.
  • the thickness of the cathode is preferably 10 nm to 500 nm, and more preferably 50 nm to 200 nm.
  • the cathode can be formed by forming a film by a commonly used method such as sputtering, ion plating, or vapor deposition.
  • IR (KBr): ⁇ 2982, 2214, 1662, 1583, 1521, 1473, 1424, 1383, 1263, 1242, 1221, 1158, 1068, 936, 889, 827, 782, 749, 673 cm ⁇ 1 .
  • the fac-tris [2- (5′-hydroxyimino-4′-methylphenyl) pyridine] iridium (III) ⁇ 2.5 hydrate 22 mg (25 ⁇ mol) obtained above was added to 2 mL of acetic anhydride for 2 hours. Stir at 140 ° C. and concentrate under reduced pressure. The obtained residue was washed with water to obtain 20 mg of fac-tris [2- (5′-cyano-4′-methylphenyl) pyridine] iridium (III) monohydrate as a yellow powder (reaction was quantitative) Advanced).
  • Example 5 (Synthesis of Compound (1-33))
  • fac-tris [2- (4′-methoxyphenyl) pyridine] iridium (III) was used instead of fac-tris [2- (4′-methylphenyl) pyridine] iridium (III).
  • fac-tris [2- (5′-formyl-4′-methoxyphenyl) pyridine] iridium (III) was synthesized. mp. > 300 ° C The structure was confirmed by 1 H NMR.
  • Example 6 (Synthesis of Compound (1-34))
  • fac-tris [2- (5′-formyl-4′-methylphenyl) pyridine] iridium (III) fac-tris [2- (5′-formyl-4′-methoxyphenyl) was used.
  • Fac-tris [2- (5′-cyano-4′-methoxyphenyl) pyridine] iridium (III) was synthesized in the same manner as above using) pyridine] iridium (III). mp. > 300 ° C The structure was confirmed by 1 H NMR.
  • fac-tris [2- (4′-methylphenyl) pyridine] iridium (III) compound A
  • JASCO-V550 and V-630BIO UV-Vis spectrometers were used for UV / visible absorption, and JASCO FP-6500 and FP-6200 spectrofluorometers were used for luminescence excitation and emission spectra, respectively.
  • Quantum efficiency ( ⁇ ) was measured as a comparison value with the integrated modified emission spectrum of standard quinine sulfate.
  • the luminous particle efficiency of standard quinine sulfate in 0.1 M sulfuric acid was assumed to be 0.55 (excitation; 366 nm). The results are shown in Table 1 below.
  • FIG. 1 shows an organic EL element 10 according to this example.
  • the organic EL element 10 includes a substrate 12, an anode 14 made of ITO, a hole injection layer 16, a hole transport layer 18, a light emitting layer 20, a hole blocking layer 22, an electron injection layer 24, and a cathode 26.
  • the transition metal complex according to this example can be contained in the light emitting layer 20.
  • the organic EL element 10 is expected to emit stable blue light with high light emission quantum efficiency.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un complexe de métal de transition qui comprend un métal de transition appartenant à l'un des groupes 8-10 et un ligand représenté par la formule générale (1), ledit ligand étant lié audit métal de transition par l'intermédiaire d'une liaison de coordination ; un matériau émettant une phosphorescence qui comprend le complexe de métal de transition ; et, à titre d'exemple de l'utilisation dudit complexe de métal de transition, un dispositif d'électroluminescence organique qui comporte une paire d'électrodes et au moins une couche organique comprenant une couche, ladite couche étant positionnée entre les électrodes et contenant une matière émettant une phosphorescence qui comprend le complexe de métal de transition. Dans la formule générale (1) : R1 et R2 représentent indépendamment un substituant ; m et n représentent indépendamment un entier de 0-4 ; Z représente un groupe fonctionnel ayant une constante de substitution de Hammett (σp) de 0-0,8 ; et # représente la position de la liaison de coordination au métal de transition.
PCT/JP2010/070749 2010-11-19 2010-11-19 Complexe de métal de transition et son utilisation WO2012066686A1 (fr)

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JP2011242372A (ja) * 2010-05-21 2011-12-01 Tokyo Univ Of Science ｐＨ指示薬およびその製造方法
WO2013018531A1 (fr) * 2011-07-29 2013-02-07 Canon Kabushiki Kaisha Complexe organométallique et élément électroluminescent comprenant celui-ci
CN103896990A (zh) * 2014-03-12 2014-07-02 石家庄诚志永华显示材料有限公司 有机电致发光材料及其应用
JP2015527338A (ja) * 2012-08-02 2015-09-17 エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Ｅｃｌ製造用の新規ビス−イリジウム錯体

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011242372A (ja) * 2010-05-21 2011-12-01 Tokyo Univ Of Science ｐＨ指示薬およびその製造方法
WO2013018531A1 (fr) * 2011-07-29 2013-02-07 Canon Kabushiki Kaisha Complexe organométallique et élément électroluminescent comprenant celui-ci
JP2015527338A (ja) * 2012-08-02 2015-09-17 エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ Ｅｃｌ製造用の新規ビス−イリジウム錯体
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CN103896990A (zh) * 2014-03-12 2014-07-02 石家庄诚志永华显示材料有限公司 有机电致发光材料及其应用

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