WO2004039914A1 - Agents luminescents - Google Patents

Agents luminescents Download PDF

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WO2004039914A1
WO2004039914A1 PCT/JP2003/013609 JP0313609W WO2004039914A1 WO 2004039914 A1 WO2004039914 A1 WO 2004039914A1 JP 0313609 W JP0313609 W JP 0313609W WO 2004039914 A1 WO2004039914 A1 WO 2004039914A1
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Prior art keywords
group
light
ring
general formula
substituent
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PCT/JP2003/013609
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English (en)
Japanese (ja)
Inventor
Hisanori Itoh
Yuji Nakayama
Yoshimasa Matsushima
Yoji Hori
Shizuo Tokito
Toshimitsu Tsuzuki
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Takasago International Corporation
Japan Broadcasting Corporation
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Priority to AU2003275645A priority Critical patent/AU2003275645A1/en
Priority to JP2005501845A priority patent/JPWO2004039914A1/ja
Priority to TW092129881A priority patent/TWI241150B/zh
Publication of WO2004039914A1 publication Critical patent/WO2004039914A1/fr

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Definitions

  • the present invention relates to a light-emitting element which can emit light by converting electric energy into light. More specifically, the present invention relates to a novel light-emitting element that can be suitably used in fields such as display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signs, and interiors. Background art
  • organic electroluminescent devices (hereinafter referred to as organic EL devices) are promising display devices because they can obtain high-luminance light at low voltage.
  • organic EL devices organic electroluminescent devices
  • a light-emitting element that forms an organic thin film by vapor deposition of an organic compound is known.
  • This light-emitting element uses a tris (8-hydroxyquinoline) aluminum complex (hereinafter referred to as A1q), which is a fluorescent material, as an electron transport material, and a hole transport material (for example, an amine compound).
  • A1q tris (8-hydroxyquinoline) aluminum complex
  • the emission process of phosphorescent light is a process in which a molecule is excited from a ground state to an excited state, and then a nonradiative transition called intersystem crossing occurs from a singlet excited state to a triplet excited state.
  • the phosphorescence shows luminescence from the triplet state to the ground state. It is expected that high luminous efficiency will be achieved by using the singlet state and triplet state of the organic phosphorescent material. This is thought to contribute to extending the life of the organic EL device.
  • An organic EL device using such a phosphorescent material includes a tris (2-phenylvinylidine) iridium complex (Ir ( ⁇ y) 3 ) which is an ortho-metallated pyridinium complex.
  • Ir ( ⁇ y) 3 2-phenylvinylidine iridium complex
  • a green light-emitting device using phosphorescent light has been reported (Applied Physics Letters, 75, 4 (1999)).
  • platinum complexes include (6-phenyl-2,2,1-vinylidene-C, N, N) platinum (II) chloride and its derivatives (EC Constable et al., J Chem. Soc. Dalton Trans., 1990, 443-449; Tsz-Chun Cheung et al., J. Chem. Soc. Dalton Trans., 1996, 1645-1651; Yurngdong Jahng et al., In organica Chimica Acta, 267 (1998) 265-270; Siu-Wai Lai et al., Inorg. Ghem., 38 (1999) 4046-4055). It has been reported that this platinum complex exhibits an ultraviolet absorption phenomenon and a fluorescence emission phenomenon.
  • Japanese Patent Application Laid-Open No. 2002-1755884 does not disclose data such as external quantum efficiency.
  • a metal coordination compound for a light-emitting element a cyclic group containing a nitrogen atom is used.
  • a platinum complex in which two cyclic groups each containing a carbon atom are coordinated is disclosed.
  • the platinum complexes specifically disclosed herein include those in which all four cyclic groups are independently coordinated to platinum, and those in which only two of the four cyclic groups are bonded. There are three types, one in which it is coordinated to platinum, and the other in which four cyclic groups are each bonded to platinum in a state where two are bonded to each other. There are no disclosures of complexes in which each of the four is coordinated to platinum in a bonded state.
  • devices that achieve high-brightness light emission are devices in which organic substances are stacked by vacuum evaporation.However, coating methods are used from the viewpoint of simplification of the manufacturing process, workability, and large area. It is desirable to produce the device by using the above method. However, a device manufactured by the conventional coating method is inferior to a device manufactured by the vapor deposition method, particularly in terms of luminous efficiency, and development of a new luminescent material is desired from such a point.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a novel light emitting element which can be used in various fields and has good light emitting characteristics and light emitting efficiency.
  • FIG. 1 is a diagram showing a configuration example of an organic EL device using the platinum complex according to the present invention. ' The description of the reference numerals in FIG. 1 is described below.
  • Second electrode metal electrode, cathode
  • the present invention has the following general formula [1]
  • any two of ring A, ring B, and ⁇ C each independently may have a substituent, and a nitrogen-containing aromatic heterocycle coordinated to a platinum atom by a nitrogen atom.
  • ⁇ ⁇ represents a group, and the rest represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and Y represents a halogen atom, or directly or oxygen atom
  • a light-emitting element containing at least one platinum complex represented by the formula a light-emitting element containing at least one platinum complex represented by the formula:
  • the platinum complex represented by the above general formula [1] include, for example, the following general formula [1 ']
  • ring A i and ring each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent
  • ring C i is an aryl group which may have a substituent
  • X represents a halogen atom
  • a platinum complex represented by the following formula:
  • Preferred examples of the platinum complex represented by the general formula [1,] include, for example, the following general formula
  • ring 0 represents an aryl group or a heteroaryl group.
  • I 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a halogenated alkyl group, an aralkyl group, an alkenyl group, Alkynyl group, aryl group, amino group, mono or dialkyl amino group, mono or diaryl amino group, alkoxy group, aryloxy group, heteroaryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, sulfamoyl group, alkylthio group, arylthio group, heteroarylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoramide group , Hydroxyl group, mercapto group,
  • a plurality of R 1 s , a plurality of R 2 s, and / or a plurality of R 3 s may be joined together to form a condensed ⁇ with a pyridine ring or a ring C to which they are bonded.
  • m 1 111 2 and 111 3 each represent the number of substituents I 1 , R 2 and R 3
  • m 1 represents an integer of 0 to 3
  • m 2 and m 3 represent an integer of 0 to 4 .
  • m ⁇ mm 3 is an integer of 2 or more
  • a plurality of 1 , a plurality of R 2, and a plurality of R 3 may be the same or different from each other. ).
  • platinum complex represented by the general formula [1 '] include, for example, the following general formula [1b,]
  • platinum complex represented by the general formula [1] include, for example, the general formula [1 ′,]
  • ring B 2 and ring C 2 each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent
  • ring A 2 may have a substituent.
  • a good aryl group or a heteroaryl group which may have a substituent, a ring B 2 and a ring C 2 , a ring C 2 and a ring A 2 , or a ring B 2 and a ring C 2 and a ring And A 2 may combine with each other to form a condensed ring. Indicates a halogen atom.
  • Preferred examples of the platinum complex represented by the general formula [1 ′,] include, for example, the following general formula [1a ,,]
  • a 2 represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent
  • R 1 and R 3 each independently represent a hydrogen atom , Alkyl group, halogenated alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, mono- or diarylamino group, alkoxy group, aryloxy group, heteroaryloxy Xy, alkoxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, heteroaryl Monothio group, sulfonyl group, sulfinyl group, ureide group, phosphoramide group, Loxyl group, mercapto group, halogen
  • m 1 and m 3 are that it substituted
  • the group represents the number of R 1 and R 3
  • m 1 represents an integer of 0 to 3
  • m 3 represents an integer of 0 to 4.
  • III 1 and m 3 are integers of 2 or more, R 2 R 3 may be the same or different from each other, and X is the same as described above.
  • platinum complex represented by Further preferred examples of the platinum complex represented by the above general formula L 1] include, for example, the following general formulas [1 ′, ′]
  • rings A 2 and ⁇ E are each independently Represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, wherein ring A 2 and ring C 2 , ring C 2 and ring B 2 Or ring A 2 , ring C 2 and ring B 2 may combine with each other to form a condensed ring, and ring A 2 , ⁇ B 2 , ring C 2 and / or E are substituted
  • the substituent is a substituent capable of coordinating or bonding a metal
  • the metal atom may be coordinated or bonded by a coordinating or bondable atom in the substituent.
  • platinum complex represented by the general formula [1, "] include, for example, the following general formula [1a ,,,]
  • R 1 and R 3 each independently represent an alkyl group, a halogenated alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, Amino group, mono- or dialkylamino group, mono- or diarylamino group, alkoxy group, aryloxy group, heteroaryloxy group, alkoxylation Rupoyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group Group, heteroarylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoramide group, hydroxyl group, mer
  • R 1 and R 3 may be taken together to form a condensed ring with the two pyridine rings to which they are attached, and R 1 and ring A 2 , and R 1 and R 3 ⁇ A 2 may be taken together to form a condensed ring.
  • m 1 and m 3 each represent the number of substituents R 1 and R 3 , m 1 represents an integer of 0 to 3, and m 3 represents an integer of 0 to 4.
  • mm 3 is an integer of 2 or more, a plurality of I 1, a plurality of R 3 is rather good be different be the same as each other, respectively, also, a plurality of R 1 s or / and a plurality of R 3 They may be joined together to form a condensed ring with the pyridine ring to which they are attached.
  • the substituent in I 1 , R 3 , ring A 2 or / and ring E is a substituent capable of coordinating a metal or capable of bonding to a metal, the coordination in the substituent The metal atom may be coordinated or bonded with a possible or bondable atom.
  • platinum complex represented by the general formula include, for example, the following general formula [1b "']
  • RRR 3 and R 4 each independently represent an alkyl group, a halogenated alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group.
  • R 1 and R 2 , R 1 and R 3 , or / and R 1 and R 2 and R 3 are combined to form two pyridine or pyridine rings and benzene ring to which they are bonded.
  • a condensed ring may be formed with the ring.
  • m ⁇ m 3 and m 4 it shows it number of substituents II 1, RR 3 and R 4, the integer m 1 is 0 ⁇ 3, m 2 and m 3 is an integer of 0-4, and , M 4 indicates an integer of 0 to 5, respectively.
  • the plurality of R, the plurality of R 2 , the plurality of R 3, and the plurality of R 4 may be the same or different from each other, and , R 1 , R 2 , R 3 , and / or R 4 may be taken together to form a condensed ring with a pyridine ring or a benzene ring to which they are bonded.
  • RRR 3 and / or R 4 is a substituent capable of coordinating a metal or capable of bonding to a metal
  • the metal atom is a coordinating or bondable atom in the substituent. May be coordinated or bonded.
  • the platinum complex represented by the general formula [1] includes a tridentate ligand consisting of ring A, ring B, and ring C, a halogen atom, or a direct or oxygen atom ( ⁇ 0—) Consisting of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a sulfur atom (-S-)
  • a complex compound (however, when two adjacent rings are nitrogen-containing aromatic heterocyclic groups, except when Y is a chlorine atom, two non-adjacent rings are nitrogen-containing aromatic heterocyclic groups In the case of, except when Y is a group other than a halogen atom.)
  • any one of ⁇ , ⁇ 3, and ring C is a ring coordinated with a platinum atom by a nitrogen atom. And the other one is a ring group bonded to a platinum atom with a carbon atom.
  • Each of these rings may be a monocyclic ring, a polycyclic ring, or a condensed ring, and even if ring A and ring C or ring C and ring B form a condensed ⁇ , ring A and ring C and ⁇ B And may form a condensed ring.
  • the platinum complex is an orthometallated platinum complex.
  • Orthometalated complexes are described in, for example, Akio Yamamoto, “Organometallic Chemistry: Fundamentals and Applications 1”, pp. 150-232, Shokabosha, 198 Published two years, by H. Yersin, "Photochemistry and Photophysics of coordinati on Compounds", by H. Yersin, pp. 71-77. Pp. 135-146, Springer-Verlag, published in 1987, and the like.
  • a nitrogen-containing aromatic heterocyclic group which may have a substituent represented by ring A, ring B and ring C, represented by ring A and ring in general formula [1,]
  • Good nitrogen-containing aromatic heterocyclic groups each independently include a nitrogen-containing aromatic heterocyclic group and a substituted nitrogen-containing aromatic heterocyclic group.
  • the nitrogen-containing aromatic heterocyclic group is, for example, a heterocyclic group having 2 to 15 carbon atoms and having at least one nitrogen atom as a hetero atom, and further having one to three nitrogen atoms, oxygen, and the like. It may have a hetero atom such as an atom or a sulfur atom.
  • the nitrogen-containing aromatic heterocyclic group is a 5- to 8-membered, preferably 5- or 6-membered, monocyclic nitrogen-containing aromatic heterocyclic group, a polycyclic or condensed-ring nitrogen-containing aromatic heterocyclic group. is there.
  • nitrogen-containing aromatic heterocycle examples include, for example, a pyridine ring, a pyrimidine ring, a pyrazine ⁇ , a pyridazine ⁇ , a pyrazolyl ring, an imidazolyl ring, an oxazolyl ring, and a thiazolyl ring.
  • a quinoline ring an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline, a naphthyridine ring, a cinnoline, a benzimidazole, a benzoxazole, a benzothiazole, and the like.
  • Examples of the substituted nitrogen-containing aromatic heterocyclic group include a nitrogen-containing aromatic heterocyclic ring in which at least one hydrogen atom of the above-mentioned nitrogen-containing aromatic heterocyclic group is substituted with a substituent.
  • a substituent The hydrocarbon group, the substituted hydrocarbon group, the aliphatic heterocyclic group, the substituted aliphatic heterocyclic group, the aromatic heterocyclic group, the substituted aromatic heterocyclic group, the alkoxy group, the substituted alkoxy group, and the aryl group.
  • Roxy group substituted aryloxy group, aralkyloxy group, substituted aralkyloxy group, heteroaryloxy group, substituted heteroaryloxy group, alkoxyl alkenyl group, aryloxycarbonyl group, aralkyloxycarbonyl Group, acyl group, acyloxy group, alkylthio group, aralkylthio group, arylthio group, heteroarylthio group, halogen atom, alkylenedioxy group, amino group, substituted amino group, hydrazino group, cyano group, ni Toro group, hydroxyl group, carboxyl group, hydroxamic acid group, sulfonylamino group, sulfamoyl Group, substituted sulfadyl group, sorbamoyl group, substituted rubamoyl group, sulfo group, sulfonyl group, sulfino group, sulfinyl group
  • hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group.
  • the alkyl group may be linear, branched or cyclic, for example, an alkyl having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • Groups specifically, methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, isopropyl, tert-butyl, n-pentyl, 2 —Pentyl group, tert —pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 2-methylpentyl Group, 3-methylpentyl group, 4-methylpentyl group, 2-methylpentane-3-yl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like
  • the alkenyl group may be linear or branched, and includes, for example, an alkenyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. Represents an ethenyl group, a propenyl group, a 1-butenyl group, a pentenyl group, a hexenyl group or the like.
  • the alkynyl group may be linear or branched, for example, an alkynyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. Specific examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, pentynyl, hexynyl and the like.
  • Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • Examples of the aralkyl group include a group in which at least one hydrogen atom of the aralkyl group is substituted with the aralkyl group. For example, an aralkyl group having 7 to 12 carbon atoms is preferable. Specific examples include a benzyl group, a 2-phenylethyl group, a 1-phenylpropyl group, and a 3-naphthylpropyl group.
  • Examples of the aliphatic heterocyclic group include, for example, those having 2 to 14 carbon atoms and at least 1 and preferably 1 to 3 hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom. Examples thereof include a 5- to 8-membered, preferably 5- or 6-membered, monocyclic aliphatic heterocyclic group or a polycyclic or fused-ring aliphatic heterocyclic group containing an atom.
  • aliphatic heterocyclic group examples include, for example, a pyrrolidyl-2-one group, a piperidino group, a piperazinyl group, a morpholino group, a tetrahydrofuryl group, a tetrahydroviranyl group, and the like.
  • Examples of the aromatic heterocyclic group include a heteroatom having 2 to 15 carbon atoms and at least one, and preferably 1 to 3 heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the alkoxy group may be linear, branched, or cyclic, and includes, for example, an alkoxy group having 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, and a 2-propoxy group. , N-butoxy, 2-butoxy, isoptoxy, tert-butoxy, n-pentyloxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropyloxy, n- Xyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methyl Examples include a tylpentyloxy group, a 5-methylpentyloxy group, and a cyclohexyloxy group.
  • aryloxy group examples include an aryloxy group having 6 to 14 carbon atoms, and specific examples include a phenyloxy group, a naphthyloxy group, and an anthroxy group.
  • aralkyloxy group examples include an aralkyloxy group having 7 to 12 carbon atoms. Specific examples thereof include a benzyloxy group, a 2-phenylethyloxy group, an 1-phenylpropoxy group, a 2-phenylpropoxy group, and a 3-phenyloxy group.
  • Enylpropoxy group 1-phenylbutoxy group, 2-phenylphenyloxy group, 3-phenylbutoxy group, 4-phenylbutoxy group, 1-phenylpentyloxy group, 2-phenylpentyloxy group, 3-phenylpentyloxy group, 4 —Phenylpentyloxy, 5-phenylphenyloxy, 1-phenylhexyloxy, 2-phenylhexyloxy, 3-phenylhexyloxy, 4-phenylhexyloxy, 5—phenylhexyloxy, 6 — A phenylhexyloxy group and the like.
  • the heteroaryloxy group includes, for example, at least one, and preferably one to three, heteroatoms containing a heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc.
  • a heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc.
  • specific examples thereof include a 2-pyridyloxy group, a 2-pyraziloxy group, a 2-pyrimidyloxy group, and a 2-quinolyloxy group.
  • the alkoxycarbonyl group may be linear, branched or cyclic, and includes, for example, an alkoxycarbonyl group having 2 to 19 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a —Propoxycarbonyl group, 2-butoxycarbonyl group, n—butoxycarbonyl group, tert—butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group And a lauryloxycarbonyl group, a stearyloxycarbonyl group, a cyclohexyloxycarbonyl group and the like.
  • Examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 to 20 carbon atoms, and specific examples include a phenyloxycarbonyl group and a naphthyloxycarbonyl group.
  • Examples of the aralkyloxycarbonyl group include an aralkyloxycarbonyl group having 8 to 15 carbon atoms, and specific examples thereof include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a 9-fluorene group. Nylmethyloxycarbonyl and the like.
  • acyl group may be linear or branched.
  • examples thereof include an acyl group having 1 to 18 carbon atoms derived from a carboxylic acid such as a fatty acid carboxylic acid and an aromatic carboxylic acid, and specifically, a formyl group, Examples include acetyl, propionyl, petyryl, bivaloyl, pentanoyl, hexanoyl, lauroyl, stearoyl, benzoyl and the like.
  • acyloxy group examples include those derived from carboxylic acids, for example, those having 2 to 18 carbon atoms.Specific examples include an acetooxy group, a propionyloxy group, a petyriloxy group, a bivaloyloxy group and a pentanoyloxy group. Xy, hexanoyloxy, lauroyloxy, stearoyloxy, benzoyloxy and the like.
  • the alkylthio group may be linear, branched, or cyclic, and includes, for example, an alkylthio group having 1 to 6 carbon atoms. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, Examples include a propylthio group, an n-butylthio group, a 2-butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, and a cyclohexylthio group.
  • arylthio group examples include an arylthio group having 6 to 14 carbon atoms, and specific examples include a phenylthio group and a naphthylthio group.
  • aralkylthio group examples include an aralkylthio group having 7 to 12 carbon atoms, and specific examples include a benzylthio group and a 2-phenethylthio group.
  • the heteroarylthio group includes, for example, at least one, and preferably one to three, heteroatoms containing a heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc., having 2 to 1 carbon atoms. And the like.
  • a heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc.
  • Specific examples include 4-heteroarylthio group, specifically, 4-pyridylthio group, 2-benzimidazolylthio group, 2-benzoxazolylthio group, 2-benzothiazolylthio group, and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. I can do it.
  • alkylenedioxy group examples include an alkylenedioxy group having 1 to 3 carbon atoms, and specific examples include a methylenedioxy group, an ethylenedioxy group, and a propylenedioxy group.
  • substituted hydrocarbon group examples include a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted aryl group, a substituted aralkyl group, and the like.
  • substituted alkyl group examples include an alkyl group in which at least one hydrogen atom of the above alkyl group is substituted with a substituent such as an alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • a substituent such as an alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • the alkyl group, the alkoxy group, and the halogen atom are the same as described above, and the substituted amino group is the same as the later-described substituted amino group.
  • alkyl group substituted by a halogen atom that is, a halogenated alkyl group
  • at least one hydrogen atom of the above alkyl group is halogenated by a halogen atom (for example, fluorination, chlorination, bromination, etc.).
  • a halogen atom for example, fluorination, chlorination, bromination, etc.
  • Iodinated, etc.) halogenated alkyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples include a methyl group, a trifluoromethyl group, a 2-chloroethyl group, a 3-bromopropyl group, and a 3,3,3-trifluoropropyl group.
  • the substituted aryl group at least one hydrogen atom of the above aryl group is substituted with a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • the alkyl group, the halogenated alkyl group, the alkoxy group, the halogen atom, the substituted amino group and the alkylenedioxy group are the same as described above, and the substituted amino group is the same as the later-described substituted amino group.
  • Specific examples of the aryl group substituted with an alkyl group include
  • Examples of the substituted aralkyl group include an aralkyl group in which at least one hydrogen atom of the aralkyl group is substituted with a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group. Two adjacent hydrogen atoms of an aryl group in an aralkyl group are substituted with a substituent such as an alkylenedioxy group. Alkyl group.
  • the alkyl group, the halogenated alkyl group, the alkoxy group, the halogen atom and the substituted amino group are the same as described above, and the substituted amino group is the same as the later-described substituted amino group.
  • a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, or a halogen atom.
  • heterocyclic groups are the same as described above.
  • a heteroaryl group in which at least one hydrogen atom of the above-mentioned heteroaryl group is substituted with a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom or the like.
  • a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom or the like.
  • Examples of the substituted alkoxy group include an alkoxy group in which at least one hydrogen atom of the above alkoxy group is substituted with a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • the alkyl group, the halogenated alkyl group, the alkoxy group and the halogen atom are the same as described above, and the substituted amino group is the same as the later-described substituted amino group.
  • the substituted aryloxy group at least one hydrogen atom of the above-mentioned aryloxy group is a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group.
  • the alkyl group, halogenated alkyl group, alkoxy group, halogen atom and alkylenedioxy group are the same as described above, and the substituted amino group is the same as the substituted amino group described later.
  • Examples of the substituted aralkyloxy group include an aralkyloxy group in which at least one hydrogen atom of the above aralkyloxy group is substituted with a substituent such as an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom, an amino group, or a substituted amino group. And an aralkyloxy group in which two adjacent hydrogen atoms of the aryl group in the above aralkyloxy group are substituted with a substituent such as an alkylenedioxy group.
  • the alkyl group, halogenated alkyl group, alkoxy group, halogen atom and alkylenedioxy group are Same as above, and the substituted amino group is the same as the substituted amino group described later.
  • the substituted amino group include an amino group in which one or two hydrogen atoms of an amino group have been substituted with a substituent such as a protecting group. Any protecting group can be used as long as it is used as an amino protecting group.
  • a substituent such as a protecting group.
  • Any protecting group can be used as long as it is used as an amino protecting group.
  • PROTECTIVE GROUPS IN 0 RGANI C SYNTHES IS Second Edition (JOHN WILEY & SONS, INC.) Examples thereof include those described as an amino protecting group.
  • amino protecting group examples include an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aralkyloxycarbonyl group.
  • the alkyl group, aryl group, aralkyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group and aralkyloxycarbonyl group are the same as described above.
  • an amino group substituted with an alkyl group that is, an alkyl-substituted amino group
  • an amino group substituted with an alkyl group include N-methylamino group, N, N-dimethylamino group, N, N-getylamino group, N, N-diisopropyl.
  • Mono or dialkylamino groups such as amino group and N-cyclohexylamino group are exemplified.
  • an amino group substituted with an aryl group that is, an aryl-substituted amino group
  • an amino group substituted with an aryl group include mono-groups such as N-phenylamino group, N, N-diphenylamino group, N-naphthylamino group, N-naphthyl-N-phenylamino group and the like. Or a diarylamino group.
  • Specific examples of the amino group substituted with an aralkyl group, that is, an aralkyl-substituted amino group include a mono- or diaralkylamino group such as an N-benzylamino group and an N, N-dibenzylamino group.
  • amino group substituted with an acyl group that is, a formylamino group, an acetylamino group, a propionylamino group, a vivaloylamino group, a pentanoylamino group, a hexanoylamino group, a benzoylamino group, and the like can be given. .
  • an amino group substituted with an alkoxycarbonyl group that is, an alkoxycarbonylamino group
  • an amino group substituted with an alkoxycarbonyl group include a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an n-butoxycarbonyl, an amino group, and a tert- group.
  • Specific examples of an amino group substituted with an aryloxycarbonyl group, that is, an aryloxycarbonylamino group include one hydrogen atom of the amino group as described above.
  • a phenoxycarbonylamino group a naphthyloxycarbonylamino group and the like.
  • Specific examples of an amino group substituted with an aralkyloxycarbonyl group, that is, an aralkyloxycarbonylamino group include a benzyloxycarbonylamino group.
  • Is a Suruhoniruamino group for example R- S 0 2 - NH- (R represents an alkyl group, a substituted alkyl group, ⁇ Li Ichiru group, a substituted Ariru group, Ararukiru group, a substituted Ararukiru group.)
  • R represents an alkyl group, a substituted alkyl group, ⁇ Li Ichiru group, a substituted Ariru group, Ararukiru group, a substituted Ararukiru group.
  • a substituted sulfonylamino group represented by The alkyl group, substituted alkyl group, aryl group, substituted aryl group, aralkyl group and substituted aralkyl group represented by R are the same as described above.
  • Specific examples of the sulfonylamino group include a methanesulfonylamino group and a p-toluenesulfonylamino
  • one or two hydrogen atoms of the amino group in the sulfamoyl group are the above alkyl group, the above substituted alkyl group, the above aryl group, the above substituted aryl group, the above aralkyl group, the above substituted aralkyl group.
  • Examples include a sulfamoyl group substituted with a substituent such as a group, and specific examples include an N-methylsulfamoyl group, an N, N-dimethylsulfamoyl group, and an N-phenylsulfamoyl group.
  • one or two hydrogen atoms of the amino group in the substituent rubamoyl group are the above alkyl group, the above substituted alkyl group, the above aryl group, the above substituted aryl group, the above aralkyl group, and the above.
  • Examples include a substituted aralkyl group and a substituted rubamoyl group such as an N-methylcarbamoyl group, an N, N-ethyl carbamoyl group, and an N-vinylcarbamoyl group.
  • sulfonyl group examples include a substituted sulfonyl group represented by R—SO 2 — (R is the same as described above).
  • Specific examples of the sulfonyl group include a methanesulfonyl group and a p-toluenesulfonyl group.
  • sulfinyl group examples include a substituted sulfinyl group represented by R—S O— (R is the same as described above).
  • Specific examples of the sulfinyl group include a methanesulfinyl group and a benzenesulfinyl group.
  • one or two hydrogen atoms of the amino group in the ureide group and / or one hydrogen atom of the amino group in the ureide group are the above-mentioned alkyl group or the above-mentioned group.
  • a peralkyl group substituted with a substituent such as a substituted alkyl group, the above-mentioned aryl group, the above-mentioned substituted aryl group, the above-mentioned aralkyl group, or the above-mentioned substituted aralkyl group.
  • Specific examples include an N-methylperido group and an N-phenylperido group. And the like.
  • At least one hydrogen atom of the phosphoric acid amide group in the phosphoric acid amide group is the above alkyl group, the above substituted alkyl group, the above aryl group or the above substituted alkyl group.
  • a substituted phosphite amide group substituted with a substituent such as an aryl group, the above-mentioned aralkyl group, or the above-mentioned substituted aralkyl group.
  • Specific examples thereof include a methacrylic acid amide group and a phenylphosphoric acid amide group. And the like.
  • substituted silyl group for example, three hydrogen atoms of the silyl group are substituted with a substituent such as the above-mentioned alkyl group, the above-mentioned substituted alkyl group, the above-mentioned aryl group, the above-mentioned substituted aryl group, the above-mentioned aralkyl group, and the above-mentioned substituted aralkyl group.
  • a trimethylsilyl group a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, and the like.
  • Examples of the polymerizable group include a group having a polymerizable double bond or a triple bond such as a vinyl group, a propenyl group, an ethynyl group, and a (meth) acryloyloxy group; for example, an oxylanyl group; Examples thereof include a cyclic ether group capable of ring-opening polymerization such as a tetrahydrofuranyl group and a tetrahydroviranyl group.
  • a substituted hydrocarbon group, a substituted aliphatic heterocyclic group, a substituted aromatic heterocyclic group, a substituted alkoxy group, a substituted aryloxy group, a substituted aralkyloxy group, a substituted heteroaryloxy group, an alkoxycarbonyl group, Aryloxycarbonyl group, aralkyloxycarbonyl group, acryl group, acryloxy group, alkylthio group, aralkylthio group, arylthio group, heteroarylthio group, alkylenedioxy group, substituted amino group, hydrazino Group, hydroxamic acid group, substituted sulfamoyl group, substitutional rubamoyl group, sulfonyl group, sulfinyl group, substituted ureido group, phosphoric amide group or substituted silyl group is a group selected from the above-mentioned substituent groups.
  • the aryl group which may have a substituent represented by ring A includes an aryl group and a substituted aryl group, and a heteroaryl group which may have a substituent. Examples thereof include a heteroaryl group and a substituted heteroaryl group.
  • the aryl group may be a monocyclic, polycyclic or condensed aryl group, for example, an aryl group having 6 to 14 carbon atoms. Examples include a phenyl group, a naphthyl group, an anthryl group and a biphenyl group.
  • Examples of the substituted aryl group include an aryl group in which at least one hydrogen atom of the aryl group is substituted with a substituent.
  • Examples of the substituent include the same groups as those described above for the substituent in the substituted nitrogen-containing aromatic heterocyclic group.
  • the heteroaryl group includes, for example, a heteroatom having 2 to 15 carbon atoms and containing at least one, preferably 1 to 3 heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom.
  • Examples of the substituted heteroaryl group include a substituted heteroaryl group in which at least one hydrogen atom of the above heteroaryl group is substituted with a substituent.
  • Examples of the substituent include the same groups as those described above in detail for the substituent in the substituted nitrogen-containing aromatic heterocyclic group.
  • condensed ring in the case where ring C and ring C are combined with each other to form a condensed ring include, for example, a 1,10-phenanthroline ring, a 4,5-diene ⁇ Zafuruoren - 9 - one ring, and the like, for example, of the fused ring in the case of forming a condensed ring rings and ring d (or ring C i ⁇ beauty ring B or ring a 2 and ring C 2 is bonded to Specific examples include a 1,7-phenanthroline ring and a 7,8-benzoquinoline ring.
  • Ring A, ⁇ C and ring B; ⁇ A ring C and ring Bi; ring B 2 , ring C 2 and ring A 2 May be bonded to each other to form a condensed ring.
  • examples of the halogen atom represented by Y include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
  • Y has an aryl group or a substituent which may have a substituent bonded directly or via an oxygen atom (- ⁇ -) or a sulfur atom (1s-).
  • the aryl group which may have a substituent and the heteroaryl group which may have a substituent may be a substituent represented by ring A
  • the same as the aryl group which may have a group and the heteroaryl group which may have a substituent are exemplified.
  • the halogen atom represented by X is, for example, a chlorine atom, a bromine atom , Iodine atom, fluorine atom and the like.
  • platinum complex according to the present invention include, for example, platinum complexes represented by the following (1, -1) to (1, -32).
  • platinum complex according to the present invention represented by the general formula include, for example, platinum complexes represented by the following (1 ,,-1) to (1 "-136).
  • platinum complex according to the present invention represented by the general formula [1 ,,,] include, for example, platinum complexes represented by the following (1 ,,, 11) to (1 ", 1-15) And the like.
  • the platinum complex according to the present invention represented by the general formula [1'] can be synthesized, for example, by the following method. , Vol. 18, Vol. 33, pp. 337-333 (1992) (Organometallics 1999, 18, 3337-3341). And a ligand such as 1,3-di (2-pyridyl) benzene by heating and stirring in a solvent such as acetic acid. Can be manufactured.
  • a ligand such as 1,3-di (2-pyridyl) benzene by heating and stirring in a solvent such as acetic acid.
  • a solvent such as acetic acid.
  • Examples of the raw material platinum compound used herein include potassium tetrachloroplatinate, lithium tetrabromoplatinate, sodium tetrachloroplatinate, and the like.
  • a Japanese product may be used.
  • reaction solvent acetic acid, 2-ethoxyethanol, acetonitrile and the like can be used as the reaction solvent, and these solvents may be added with water and reacted as a water-containing solvent.
  • the reaction can be performed at a reaction temperature of 30 to 150 ° C, preferably 70 to 100 ° C.
  • the platinum complex obtained in this process is usually a hydrate, and is used as a light emitting device material because it is difficult to purify such as sublimation and contains water in this state. I can't.
  • halogen atom bonded to the platinum complex hydrate is treated with a Grignard reagent containing another halogen atom at 0 to 80 ° C, preferably 10 to 80 ° C.
  • a temperature of about 40 ° C a temperature of about 40 ° C, hydration water can be removed and halogen atoms can be exchanged at once.
  • an alkyl Grignard reagent or an aryl Grignard reagent can be used, but an aryl Grignard reagent is preferred, and a phenyl Grignard reagent is particularly preferred.
  • ring B and C each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent
  • ring A 2 may have a substituent Aryl group or substitution A heterocyclic group which may have a group, wherein ring B 2 and ring C 2 , ring C 2 and ring A 2 , or ring B 2 and ring C 2 and ring A 2 are bonded to each other Condensation ⁇ may be formed.
  • the compound can be easily synthesized by reacting with the compound represented by).
  • the general formula [2] which is easily available or easily synthesized
  • the object is achieved by reacting a platinum diene complex represented by the following formula, a compound represented by the general formula [3], and a halogenating agent for introducing a desired halogen atom.
  • the platinum-gen complex represented by the general formula [2], the compound represented by the general formula [3], and a halogenating agent for introducing a desired halogen atom are allowed to react together in the presence of the platinum-gen complex represented by the general formula [2].
  • a platinum-gen complex represented by the general formula [2] is reacted with a compound represented by the general formula [3], and then a desired halogen atom is introduced.
  • a halogenating agent may be reacted.
  • the product may not be isolated after the first reaction and the second step may be performed in one pot, and the efficiency is more efficient in one pot. Targeted and preferred.
  • the platinum complex represented by the general formula [1 ′,] having a desired halogen atom is already produced.
  • the platinum complex that is, the platinum complex represented by the general formula [1] having another halogen atom is directly reacted with a halogenating agent for introducing a desired halogen atom. Just do it.
  • examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
  • the two halogen atoms represented by X may be the same or different, but the same halogen atom is preferable, and further, from the viewpoint of ease of synthesis, More preferably, these identical halogen atoms are chlorine atoms.
  • the non-conjugated diene compound represented by D may be cyclic or non-cyclic.
  • the non-conjugated diene compound is a cyclic non-conjugated diene compound, a monocyclic, polycyclic, condensed cyclic, Any of cross-linked rings may be used.
  • non-conjugated The non-conjugated compound may be a non-conjugated diene compound substituted with a substituent, that is, a substituted non-conjugated diene compound.
  • the substituent is not particularly limited as long as it does not adversely affect the production method. Examples of the substituent include those described above in the description of the substituent of the substituted nitrogen-containing aromatic heterocyclic group. The same groups as the groups can be mentioned.
  • non-conjugated diene compounds among them, 1,5-cyclooctadiene, bicyclo [2,2,1] hepter 2,5-diene, 1,5-hexadiene and the like are preferable, and more preferable non-conjugated diene compounds are , 1,5-hexadiene and the like.
  • the compound represented by the general formula [3] which is reacted with the platinum diene complex represented by the general formula [2] comprises a ring B 2 , a ring C 2 and a ring A compound having A 2, which has a function of coordinating to a platinum atom in ring B 2 and ring C 2 and bonding to a platinum atom with a carbon atom on A 2 .
  • Preferred specific examples of the compound represented by the general formula [3] include, for example, those described above.
  • platinum complex orthometallated platinum complex having a tridentate ligand and having a halogen atom
  • 1 "-1) to (1" -36 From the structural formula of formula (1) except for platinum and halogen atoms.
  • a platinum complex represented by the general formula having a desired halogen atom when it is difficult to obtain or difficult to synthesize, a platinum gen complex represented by the general formula [2] having a desired halogen atom is represented by:
  • the halogenating agent used when it is difficult to obtain or difficult to synthesize are, for example, metal halides and halogens.
  • inorganic halogenating agents such as phosphorus halides and organic halogenating agents.
  • the metal halide include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, and sodium iodide.
  • Alkali metal halides such as potassium fluoride, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, magnesium fluoride, chloride
  • alkaline earth metal halides such as magnesium, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, and calcium iodide.
  • Examples of the phosphorus halide include phosphorus trichloride and phosphorus tribromide.
  • Examples of the halogens include halogens such as fluorine, chlorine, bromine, and iodine.
  • organic halogenating agent examples include succinic acid imids such as N-chlorosuccinic acid imid and N-bromosuccinic acid imid.
  • metal halides are particularly preferred.
  • a platinum-gen complex represented by the general formula [2] (hereinafter abbreviated as a platinum-gen complex [2]) and a compound represented by the general formula [3] (hereinafter abbreviated as compound [3])
  • platinum complex C 1 This is a formula for explaining a method for producing a platinum complex represented by the following general formula (hereinafter, abbreviated as platinum complex C 1 ").
  • the platinum complex can be easily produced by reacting the platinum diene complex [2] with the compound [3] in the presence of a suitable solvent, if necessary, in an inert gas atmosphere. In the production method, the reaction may be carried out by using an ultrasonic generator as needed.
  • the amount of the platinum gen complex [2] and the compound [3] to be used is generally 0.5 to 20 equivalents, preferably 0.8 to 5 equivalents, of the compound [3] with respect to the platinum gen complex [2]. It is appropriately selected from the boxes.
  • Production method 1, ' is preferably performed in the presence of a solvent.
  • the solvent examples include amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, cyano-containing compounds such as acetonitrile, dichloromethane, and 1,2.
  • amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, cyano-containing compounds such as acetonitrile, dichloromethane, and 1,2.
  • amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide
  • cyano-containing compounds such as acetonitrile, dichloromethane, and 1,2.
  • Hydrocarbons such as dichlorobenzene, aliphatic hydrocarbons such as pendant, hexane, heptane, octane, decane, cyclohexane, benzene
  • solvents may be used alone or in an appropriate combination of two or more.
  • Preferred solvents include ethylene glycol getyl ether, tetrahydrofuran, ethers such as 1,4-dioxane and 1,3-dioxolan, etc., acetone, methylethylketone, methylisobutylketone, and cyclohexane.
  • Ketones such as hexanone
  • alcohols such as methanol, ethanol, 2-propanol, n-butanol and 2-ethoxyethanol
  • polyvalents such as ethylene glycol, propylene glycol, 1,2-propanediol, and glycerin Examples include alcohols and water.
  • the amount of the solvent to be used is not particularly limited as long as the reaction can proceed sufficiently, but it is usually 1 to 200 times, preferably 1 to 50 times the volume of the platinum-gen complex [2].
  • Production methods 1 and 2 are preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas.
  • the reaction temperature is appropriately selected usually from 25 to 300 ° (preferably from 60 to 200 ° C., more preferably from 80 to 150 ° C.).
  • the reaction time varies depending on the reaction temperature and other reaction conditions, but is usually 10 minutes.
  • Scheme 2 shows a platinum complex having a desired halogen atom [1,1], which reacts a platinum-gen complex [2] with a compound [3] and a halogenating agent for introducing a desired halogen atom. '] (Hereinafter, this is referred to as a platinum complex [1 d',].).
  • the platinum complex [1d ,,] is prepared by mixing a platinum-diene complex [2], a compound [3] and a halogenating agent for introducing a desired halogen atom, in the presence of a suitable solvent, if necessary. It can be easily produced by reacting in an inert gas atmosphere. First, the platinum-gen complex [2] and the compound [3] are reacted in the presence of a suitable solvent, if necessary, in an inert gas atmosphere. isolated and then, the presence of a platinum complex obtained [1 '5] appropriate solvent, if necessary in an inert gas atmosphere, it is reacted with a halogenating agent to introduce the desired halogen atom Can easily obtain a platinum complex [Id].
  • the platinum complex obtained by reacting the platinum-gen complex [2] with the compound [3] is subjected to post-treatment such as isolation.
  • the reaction between platinum-gen complex [2] and compound [3] By adding the halogenating agent directly into the reaction system (ie, by reacting in one pot), the platinum complex [1d,] can be produced more efficiently and easily. it can.
  • the halogenating agent may be added as it is to the reaction system, or may be added after being dissolved in a solvent. Further, a solvent may be added as needed.
  • the types of the halogenating agent and the preferred halogenating agent used in the above production method are as described above.
  • the amount of the halogenating agent to be used is appropriately selected usually from the range of 1 to 100 equivalents, preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents to the platinum complex.
  • halogenating agent used here because it is a halogenating agent to introduce the desired halogen atom, an X ⁇ X 3 of course. That is, when X of the platinum-gen complex [2] is C 1 (chlorine atom), a halogenating agent other than the chlorinating agent (chloride) (a fluoride, a bromide, an iodine) is used as the halogenating agent. Compound).
  • halogenating agent F (fluorine atom)
  • a halogenating agent chloride, bromide, iodide, etc.
  • B r bromine atom
  • the halogenating agent is a halogenating agent other than a brominating agent (bromide) (fluoride, chloride, iodide, etc.)
  • X I
  • halogenating agent fluoride, chloride, bromide, etc.
  • iodination agent iodide
  • the amounts of platinumgen complex [2] and compound [3] used are the same as those in Production method 1, '.
  • the type of solvent is the same as that of Production method 1.
  • the amount of the solvent to be used is not particularly limited as long as the reaction can proceed sufficiently. However, when a mixture of the platinum-gen complex [2], the compound [3] and the halogenating agent is reacted, The amount of the solvent used when first reacting the gen complex [2] with the compound [3] is the same as that in Production method 1. Further, once the platinum complex formed by the reaction of the platinum-gen complex [2] with the compound [3] is once isolated, the amount of the solvent in the subsequent reaction is usually 1 to 1 with respect to the platinum complex.
  • the capacity is appropriately selected from the range of 200 times the capacity, preferably from 1 to 50 times the capacity.
  • Platinum diene complex [2], compound [3] and halogenating agent are mixed and reacted.
  • the reaction temperature and reaction time in the case of first reacting the platinum-gen complex [2] with the compound [3] may be the same as those in Production method 1 '.
  • the reaction temperature of the platinum complex [1] with the halogenating agent is usually 25 to 300 ° C, preferably 60 to 200 ° C.
  • the reaction time is generally selected from the range of 10 minutes to 72 hours, preferably 30 minutes to 48 hours, more preferably 1 to 50 hours. It is appropriately selected from the range of time to 12 hours.
  • the reaction time when the reaction of the platinum-gen complex [2] with the compound [3] and the subsequent reaction with the halogenating agent is performed in one pot the reaction time of the platinum-gen complex [2] and the compound [3] 10 minutes to 72 hours, preferably 30 minutes to 48 hours, more preferably 1 hour to 12 hours after the start of the reaction with Usually, it should be performed for 10 minutes to 72 hours, preferably for 30 minutes to 48 hours, and more preferably for 1 to 12 hours.
  • reaction may be carried out using an ultrasonic generator as needed.
  • any of the production methods 2 ′ is performed in an inert gas atmosphere, but the same inert gas as that of the production method 1 ”can be used.
  • Scheme 3 shows a method for producing a platinum complex [1d “] (a platinum complex [1 ,,] having a desired halogen atom) using a platinum complex [1"] as a raw material compound (hereinafter abbreviated as Production Method 3 "). ) Is an equation describing.
  • the platinum complex [Id "] is obtained by using the platinum complex [1, '] obtained in the above-mentioned production method 1, in the presence of an appropriate solvent, and if necessary, under an inert gas atmosphere. It can be easily produced by reacting a halogenating agent to introduce a halogen atom. Can be.
  • the type and amount of the halogenating agent used, the type of the halogenating agent used, the type and amount of the solvent used, the reaction temperature, the reaction time, and the like are the same as those in the halogenation step in Production Method 2.
  • the reaction may be carried out by using an ultrasonic generator as needed. Also, the production method 3 is preferably carried out in an inert gas atmosphere, but the same inert gas as in the production method 1 can be used.
  • X 1 represents a fluorine atom, a bromine atom or an iodine atom.
  • platinum-diene complex [2] and the compound [3] used in the above-mentioned production methods 1 '"to 3," commercially available products or those appropriately produced may be used.
  • the platinum complex thus obtained can be subjected to post-treatment, isolation and purification, if necessary.
  • the post-treatment method include extraction of a reaction product, filtration of a precipitate, crystallization by addition of a solvent, and evaporation of the solvent. These post-treatments can be performed alone or in combination as appropriate.
  • Methods for isolation and purification include, for example, column chromatography, recrystallization, sublimation, etc., and these can be used alone or in combination as appropriate.
  • the platinum complex according to the present invention represented by the general formula [1, "] includes, for example, a platinum diene complex represented by the general formula [2b] and a compound represented by the general formula [3] And to form a platinum complex represented by the above general formula [1c ',].
  • E represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent
  • X 2 represents a halogen atom.
  • the platinum complex according to the present invention represented by the general formula [1 ','] also has, for example, the general formula [5]
  • a compound represented by the general formula [3] is reacted with a platinum compound represented by the general formula [3] to obtain a compound represented by the general formula [3] It can also be obtained by treating the platinum complex represented by 1c "] with a Grignard reagent represented by the general formula [4].
  • the platinum complex according to the present invention represented by the general formula [1, ''] is, for example, a platinum diene complex represented by the above general formula [2b] and a platinum complex represented by the above general formula [4].
  • the reaction can also be carried out by reacting a Grignard reagent and then reacting the compound with the compound represented by the general formula [3].
  • the platinum complex according to the present invention represented by the general formula can be produced, for example, by the following production methods 1, 2 ′ to 3 ′′.
  • the platinum complex represented by the above general formula [lc ′,], for example, a chromophore (6-Fe2,2,2,1) is obtained by stirring and reacting for hours to several days, preferably 2 hours to 1 day. Bipyridine) Platinum is obtained.
  • a Grignard reagent represented by the above general formula [4], for example, phenylmagnesium bromide is added thereto at a reaction temperature of 0 to 100 ° C, preferably 20 to 80 ° C.
  • the platinum complex according to the present invention represented by the general formula [1, ',], for example, [6-phenylene] 2,2,1-Bibidinato (C, ⁇ , ⁇ )] phenylplatinum (II) can be obtained.
  • These reactions are preferably carried out in an inert gas such as nitrogen or argon. Manufacturing method 2 ','
  • a Te Torakuro port chloroplatinic acid force re U beam represented by the above general formula [3] compounds, such as 6-phenylene Lou 2, 2 5 - Viviridine in a solvent such as acetic acid at a reaction temperature of 50 ° C. to 150 ° C., preferably 80 ° C .; up to 120 ° C. for 1 hour
  • a Grignard reagent represented by the general formula [4] is reacted therewith in the same manner as in the above production method 1 ′ , to give a platinum complex according to the present invention represented by the general formula [1], for example, [6-phenyl 2,2,-vibiliginato (C, N, N)] Phenylplatinum (II) can be obtained.
  • These reactions are also preferably performed in an inert gas such as nitrogen or argon.
  • the reaction temperature is 0 to 100 ° (preferably, 20 to 80 ° C for 30 minutes to 4 hours, preferably 1 to 3 hours.
  • the platinum diene complex represented by the general formula [2b] is, for example, a platinum compound such as potassium tetraplatoate and, for example, 1,5-hexadiene 1,5-cyclooctadiene. And a solvent such as acetic acid, 2-ethoxyethanol, or acetonitrile at a reaction temperature of 50 ° C to 140 ° C for 15 minutes to 3 hours. Can be obtained more easily.
  • a platinum compound used as a raw material include potassium tetratetrachloroplatinate, sodium tetrachloroplatinate, sodium tetrachloroplatinate, and the like. A thing may be used.
  • Acetic acid, 2-ethoxyethanol, acetonitrile and the like are used as a reaction solvent, and water may be added to these solvents to be reacted as a water-containing solvent.
  • the light-emitting device of the present invention is not particularly limited as long as it uses the platinum complex according to the present invention, such as a system, a driving method, and a use form. Devices used as charge transport materials are preferred.
  • an organic EL element As a typical light emitting element, an organic EL element can be cited.
  • the method for forming the organic layer of the light emitting device of the present invention containing the platinum complex represented by the general formula [1] according to the present invention is not particularly limited, but includes resistance heating evaporation, electron beam, and sputtering.
  • a method such as a molecular lamination method, a coating method, or an injection method is used, and resistance heating evaporation and a coating method are preferred in terms of characteristics and production.
  • the light emitting device of the present invention containing the platinum complex represented by the general formula [1] according to the present invention has a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of positive and negative electrodes. It is a device and may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, etc. in addition to the light emitting layer, and each of these layers has other functions. It may be a thing. Various materials can be used for forming each layer.
  • the anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like, and can be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof.
  • the material has a work function of 4 eV or more.
  • Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (hereinafter abbreviated as ITO), or metals such as gold, silver, chromium, and nickel.
  • the thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 zm, more preferably in the range of 501 to 1111, and still more preferably in the range of 100 to 5 nm. 0 O nm.
  • the anode one having a layer formed on a soda lime glass, an alkali-free glass, a transparent resin substrate or the like is usually used.
  • glass it is preferable to use non-alkali glass for the material in order to reduce ions eluted from the glass.
  • soda lime glass it is preferable to use a glass coated with a barrier coat such as silica.
  • the thickness of the substrate is not particularly limited as long as it is enough to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more.
  • Various methods are used to fabricate the anode depending on the material.
  • ITO in the case of ITO, electron beam method, sputtering method, resistance heating evaporation method, chemical reaction method (sol-gel method, etc.), ITO dispersion
  • the film is formed by a method such as coating.
  • the anode can be cleaned or otherwise treated to lower the device drive voltage and increase luminous efficiency.
  • I T0 UV-ozone treatment and plasma treatment are effective.
  • the cathode supplies electrons to the electron injection layer, the electron transport layer, the light-emitting layer, and the like.
  • the cathode has good adhesion, ionization potential, and stability with layers such as the electron injection layer, the electron transport layer, and the light-emitting layer that are in contact with the negative electrode. It is selected in consideration of gender.
  • metals, alloys, metal halides, metal oxides, electrically conductive compounds, or mixtures thereof can be used as the material for the cathode. Specific examples include alkalis such as lithium, sodium, and potassium.
  • the cathode may have a laminated structure containing the above compound and mixture.
  • the thickness of the cathode film can be selected as appropriate depending on the material, but is usually in the range of 1 O nm to 5 m.
  • the cathode More preferably, it is from 500 nm to 1 ⁇ m, and even more preferably from 100 nm to 1 ⁇ m.
  • Methods such as electron beam method, sputtering method, resistance heating evaporation method, and coating method are used to fabricate the cathode, and it is possible to deposit metal alone or to deposit two or more components simultaneously. . Further, it is possible to form a pole with an alloy by vapor-depositing a plurality of metals at the same time, or an alloy prepared in advance may be vapor-deposited. It is preferable that the sheet resistance of the cathode and the anode be low.
  • the material of the light emitting layer is a layer having a function of injecting electrons from the anode or the hole injection layer or the hole transport layer when an electric field is applied, and a function of providing a field for recombination of holes and electrons to emit light. Anything that can be formed may be used.
  • a fluorescent material and a phosphorescent material having high light emission efficiency can be doped in the light emitting layer.
  • benzoxazole derivatives triphenylamine derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetrahydrobutadiene derivatives, naphthalimid derivatives, Kumari derivatives Derivatives, perylene derivatives, perinone derivatives, oxazinediazole derivatives, aldazine derivatives, villaridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyropyridine derivatives, thiadiazopyridines Derivatives, styrylamine derivatives, aromatic dimethylidene compounds, metal complexes of 8-quinolinol derivatives, various metal complexes represented by rare earth complexes, polythiophene, polyphenylene, polyphenylene Examples include polymer compounds such as n-vin
  • the thickness of the light emitting layer is not particularly limited, it is usually In n! The range is preferably from 5 nm to 5 zm, more preferably from 5 nm to l ⁇ m, and still more preferably from 10 nm to 500 nm.
  • the method for forming the light-emitting layer is not particularly limited, but includes an electron beam method, a sputtering method, a resistance heating evaporation method, a molecular laminating method, and a coating method (spin coating method, cast method, dip coating method). Methods, such as an injection method and an LB method, and are preferably resistance heating evaporation and a coating method.
  • the material of the hole injection layer and hole transport layer has the function of injecting holes from the anode and transporting holes It has only to have either a function to perform the operation or a function to block the electrons injected from the cathode.
  • Specific examples include carbazole derivatives, triazole derivatives, oxadiazole derivatives, oxazole derivatives, imidazolyl derivatives, polyarylalkane derivatives, pyrazoline derivatives, birazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Amino-substituted chalcone derivatives, styryllanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilpene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds Compound, polysilane-based compound, poly (N-vinylcarbazole) derivative, aniline
  • the thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually preferably in the range of lnm to 5 / m, more preferably in the range of 5 nm to lm, and still more preferably. Is ⁇ ⁇ ⁇ ⁇ ! ⁇ 500 nm.
  • the hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the hole injecting layer and the hole transporting layer can be formed by a vacuum evaporation method, an LB method, or a method of dissolving or dispersing the above hole injecting and transporting agent in a solvent and coating (spin coating method, casting method). Methods, the divcoat method, etc.) and the ink-jet method.
  • the coating method it can be dissolved or dispersed together with the resin component.
  • the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, and polyphenylene.
  • Nylene oxide polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethylcellulose, vinyl acetate, ABS resin, alkyd resin, epoxy resin, silicone resin, etc. Is mentioned.
  • the material of the electron injecting layer and the electron transporting layer may be any material having any of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode.
  • the ionization potential of the hole blocking layer having a function of blocking holes injected from the anode is selected to be higher than the ionization potential of the light emitting layer. Specific examples include triazole derivatives, oxazole derivatives, polycyclic compounds, heteropolycyclic compounds such as bathocuproine, oxadiazole derivatives, fluorenone derivatives, diphenylquinone derivatives, and thiopyrandioxide.
  • anthraquinone dimethane derivatives anthrone derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyryl virazine derivatives, naphthalene, perylene, etc., aromatic tetracarboxylic anhydrides, phthalocyanine derivatives, 8-quinolinol derivatives
  • the thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually preferably in the range of lnm to 5 ⁇ m, more preferably 5 nm or more, and still more preferably 10 nm. nm to 50 O nm.
  • the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • Examples of the method for forming the electron injection layer and the electron transport layer include a vacuum deposition method and an LB method, and a method of dissolving or dispersing the above hole injection / transport agent in a solvent and coating (spin coating method, casting method).
  • the coating method it can be dissolved or dispersed together with the resin component.
  • the resin component those exemplified in the case of the hole injection layer and the hole transport layer can be applied.
  • any material may be used as long as it has a function of preventing a substance that promotes element deterioration such as moisture or oxygen from entering the element.
  • Specific examples include metals such as indium, tin, lead, gold, silver, copper, aluminum, titanium, nickel, magnesium oxide, silicon oxide, dialuminum trioxide, germanium oxide, nickel oxide, calcium oxide, Metal oxides such as barium oxide, diiron trioxide, ytterbium trioxide, titanium oxide, magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride metal fluoride, polyethylene, polypropylene, polymethylmethacrylate Relate, polyimide, polyurea, polytetrafluoroethylene, polychlorinated trifluoroethylene, polydichlorodifluoroethylene, copolymerized trichlorofluoroethylene, copolymer of ethylene and dichlorodifluoroethylene, tetrafluoroethylene Orochiren and at least
  • the method of forming the protective layer There is no particular limitation on the method of forming the protective layer.
  • vacuum deposition sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma, etc.
  • the polymerization method high frequency excitation ion-bratting method
  • plasma CVD method laser CVD method
  • thermal CVD method thermal CVD method
  • gas source CVD method gas source CVD method
  • coating method can be applied.
  • a platinum complex (1 ', -2) obtained in the same manner as in Reference Example 8 was placed in a Schlenk flask.
  • Pentyfluorophenyl (1,5-cyclohexene) synthesized in the same manner as in (2) above 0.8 g of platinum (II) chloride, 6-phenyl-2- (2-pyridyl) pyridine 0.3 g and 20 mL of acetic acid were charged and stirred at 80 ° C for 2 days. The obtained orange solution was concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: toluene / chloroform 1/1) to obtain the platinum complex (1 ,,,-1) of the present invention. 0.485 g was obtained as an orange solid. Yield: 51.7%.
  • the solution was extracted with ethyl ether, the solvent was distilled off, and the obtained oil was oxidized with 600 ml of an aqueous solution of 220 mg of potassium permanganate.
  • anode (IT0) (f), a hole transport layer (e), a light emitting layer (d) composed of a host material and a dopant material, and a hole block layer (C), an electron transport layer (b) and a cathode (A1 / LiF) (a) are formed in order from the glass substrate (g) side, and an anode (f) and a cathode In (a), each lead wire is connected so that a voltage can be applied between the anode (f) and the cathode (a).
  • the anode (f) is an IT0 film and is attached to a glass substrate (g).
  • the hole transport layer (e) is composed of the following compound (a—NPD)
  • the light-emitting layer (d) containing a phosphorescent light-emitting material doped with a host material is composed of the following compound (CBP),
  • the hole blocking layer (c) is composed of the following compound (BCP)
  • the electron transport layer (b) was formed of A1q with a thickness of 35 nm by a vacuum evaporation method.
  • the cathode (a) was composed of a laminate in which LiF was formed to 0.5 nm and Al was formed to 160 nm in order from the electron transport layer (b) side.
  • the degree of vacuum when vacuum-depositing the organic compound layers and the cathode layers of the organic EL devices according to Examples 1 to 3 was 8 ⁇ 10 15 Pa.
  • the external quantum efficiency of light emitted by the organic EL device (the number of charges injected into the device, (Calculated by the ratio of the number of photons) was as high as 2.2% at a luminance of 100 cd / m 2 .
  • Example 1 A compound (1′-1) obtained in Reference Example 4 or a compound (1,1-3) obtained in Reference Example 6 was used in place of the compound (1′-1 2) in Example 1.
  • Example 2 A compound (1′-1) obtained in Reference Example 4 or a compound (1,1-3) obtained in Reference Example 6 was used in place of the compound (1′-1 2) in Example 1.
  • Example 4 and Example 5 were produced in the same manner as in Example 1. Similarly, Compound (1 5 - 3) with 6% to prepare a device of Example 6. These EL characteristics were evaluated.
  • Example 7 having the same device structure as that of Example 2 except that the amount of the platinum complex (1, '-121) in the light-emitting layer (d) was 6% was prepared. Also, as in Example 2 Example 8 and Example 9 in which the light emitting layer (d) was doped with 3% and 6% of the platinum complex (1 ′, ⁇ 3) obtained in Reference Example 13 . Further, it has the same device structure as in Example 2, and the light emitting layer (d) has the platinum complex obtained in Reference Example 17
  • Example 1 1 (1 "A 1 0) and 3% doped Example 1 0 element, Reference Example 1 8 obtained in platinum complex (1 3, one 1 5) 3% de one flop the Example 1 1 was manufactured.
  • the light emitting device containing the specific orthometalated platinum complex according to the present invention can be applied to the production of various display devices, in particular, highly efficient materials for organic EL devices.

Abstract

La présente invention concerne des agents luminescents qui comprennent des complexes de platine représentés par la formule (1) dans laquelle deux éléments quelconques parmi A, B et C représentent indépendamment un groupe hétérocyclique aromatique azoté éventuellement substitué coordonné à l'atome de platine au niveau de l'atome d'azote, alors que le troisième élément représente hétéroaryle ou aryle éventuellement substitué; et Y représente halogéno ou un groupe hétéroaryle ou aryle éventuellement substitué qui est lié soit directement soit par oxygène ou soufre (à condition que lorsque deux anneaux adjacents sont des groupes hétérocycliques aromatiques azotés, les cas où Y représente chloro sont exceptés, alors que lorsque deux anneaux non adjacents sont des groupes hétérocycliques aromatiques azotés, les cas où Y ne représente pas halogéné sont exceptés). Formule (1)
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JP2012530077A (ja) * 2009-06-16 2012-11-29 ヴァーシテック・リミテッド 白金（ｉｉ）イソキノリン−ピリジン−ベンゼン系錯体、その製造方法、及びそれから作成した有機発光ダイオード
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CN107033189A (zh) * 2017-05-04 2017-08-11 南京工业大学 一种铂(ii)配合物及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000070655A2 (fr) * 1999-05-13 2000-11-23 The Trustees Of Princeton University Dispositifs electroluminescents organiques a tres haute performance utilisant l'electrophosphorescence
US20020179885A1 (en) * 2001-03-08 2002-12-05 Chi-Ming Che Organometallic light-emitting material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000070655A2 (fr) * 1999-05-13 2000-11-23 The Trustees Of Princeton University Dispositifs electroluminescents organiques a tres haute performance utilisant l'electrophosphorescence
US20020179885A1 (en) * 2001-03-08 2002-12-05 Chi-Ming Che Organometallic light-emitting material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QINDE LUI ET AL: "New red-orange phosphorescent/electrolumine scent cycloplatinated complex of 2, 6-bis(2'-indolyl) pyridine", J. CHEM. SOC. DALTON TRANS, no. 16, 18 July 2002 (2002-07-18), pages 3234 - 3240, XP002975889 *
SUI-WA LAI ET AL: "Probing d8-d8 interactions in luminescent mono and binuclear cyclometalated platinum (II) complexes of 6-phenyl-2, 2'-bipyridines", INORG.CHEM, no. 38, 1999, pages 4046 - 4055, XP002975890 *

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