JP2008266163A - Transition metal complex compound and organic electroluminescence device using the same - Google Patents

Abstract

（Ｌ^１）−Ｌ^２）−Ｌ^３）は架橋三座配位子、Ｘは、酸解離定数が１５以下の酸性化合物の共役塩基を表す。）有機ＥＬ素子は、有機薄膜発光層に該遷移金属錯体化合物を含有する。
【選択図】なしAn organic EL device that emits blue light with high luminous efficiency and a novel transition metal complex compound that realizes the organic EL device.
A transition metal complex compound having a carbene bond, for example, a transition metal complex having a metal carbene bond represented by the following formula (2).

(L ¹ ) -L ² ) -L ³ ) represents a crosslinked tridentate ligand, and X represents a conjugate base of an acidic compound having an acid dissociation constant of 15 or less. ) The organic EL device contains the transition metal complex compound in the organic thin film light emitting layer.
[Selection figure] None

Description

  The present invention relates to a transition metal complex compound and an organic electroluminescence device using the same, and more particularly to an organic electroluminescence device having high luminous efficiency and emitting blue light and a novel transition metal complex compound that realizes the same.

An organic electroluminescence (EL) element is a self-luminous element utilizing the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. . Eastman Kodak's C.I. W. Organic materials have been constructed since Tang et al. Reported on low voltage drive organic EL elements using stacked elements (CW Tang, SA Vanslyke, Applied Physics Letters, 51, 913, 1987, etc.) Research on organic EL elements as materials has been actively conducted. Tang et al. Use tris (8-hydroxyquinolinol aluminum) for the light emitting layer and a triphenyldiamine derivative for the hole transport layer. The advantages of the stacked structure are that it increases the efficiency of hole injection into the light-emitting layer, blocks the electrons injected from the cathode, increases the generation efficiency of excitons generated by recombination, and generates in the light-emitting layer For example, confining excitons. As in this example, the element structure of the organic EL element includes a hole transport (injection) layer, a two-layer type of an electron transport light emitting layer, or a hole transport (injection) layer, a light emitting layer, and an electron transport (injection) layer A three-layer type is well known. In such a stacked structure element, the element structure and the formation method are devised in order to increase the recombination efficiency of injected holes and electrons.
As light-emitting materials for organic EL elements, chelate complexes such as tris (8-quinolinolato) aluminum complex, luminescent materials such as coumarin derivatives, tetraphenylbutadiene derivatives, distyrylarylene derivatives, oxadiazole derivatives and the like are known. It is reported that light emission in the visible region from blue to red can be obtained, and realization of a color display element is expected (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, etc.).

In recent years, it has also been proposed to use a phosphorescent material in addition to a fluorescent material for the light emitting layer of an organic EL element (see, for example, Non-Patent Document 1 and Non-Patent Document 2). Thus, high emission efficiency is achieved by utilizing the singlet state and triplet state of the phosphorescent material in the light emitting layer of the organic EL element. When electrons and holes are recombined in an organic EL device, it is considered that singlet excitons and triplet excitons are generated at a ratio of 1: 3 due to the difference in spin multiplicity. If the light emitting material is used, it is conceivable that the light emission efficiency is 3 to 4 times that of an element using only fluorescence.
In such an organic EL element, an anode, a hole transport layer, an organic light emitting layer, an electron transport layer (hole blocking layer) are sequentially arranged so that the triplet excited state or triplet exciton is not quenched. A structure in which layers are stacked such as an electron transport layer and a cathode is used, and a host compound and a phosphorescent compound have been used for an organic light emitting layer (see, for example, Patent Document 4 and Patent Document 5). These patent documents are technologies related to phosphorescent materials that emit red to green light. Moreover, the technique regarding the luminescent material which has a blue luminescent color is also released (for example, refer patent document 6, patent document 7, patent document 8). However, they have a very short element lifetime, and in particular, Patent Documents 7 and 8 describe a ligand skeleton in which an Ir metal and a phosphorus atom are bonded. Although the emission color is blue, the bond is weak and heat-resistant. Sexually poor. Similarly, Patent Document 9 describes a complex in which an oxygen atom and a nitrogen atom are bonded to the central metal, but there is no description about the specific effect of the group bonded to the oxygen atom, and it is unclear. Patent Document 10 discloses a complex in which nitrogen atoms contained in different ring structures are bonded to a central metal one by one, and an element using the same emits blue light, but has an external quantum efficiency as low as about 5%. It has become.

On the other hand, in recent years, studies have been made on transition metal complex compounds having a metal carbene bond (hereinafter sometimes referred to as carbene complexes) (see, for example, Patent Document 11 and Non-Patent Documents 3 to 11).
A carbene is a two-coordinate carbon that has two electrons in the sp ² hybrid orbit and the 2p orbital, and can take four types of structures depending on the combination of the orbit into which the two electrons enter and the spin direction. Is a singlet carbene, consisting of a sp ² hybridized occupied orbit and an empty 2p orbit.
Specific examples of complexes having a carbene iridium bond include the following non-patent document 12 (tris (carbene) iridium complex comprising a non-heterocyclic carbene ligand) and non-patent document 13 (monodentate monocarbene). Iridium Complex), but application to the organic EL element field or the like is not described.
Patent Document 11 discloses the synthesis of an iridium complex having a carbene bond and its emission wavelength and device performance. However, the energy efficiency and external quantum efficiency are low, and the emission wavelength is distributed in the ultraviolet region. The sensitivity is poor. Therefore, it is not suitable for a light emitting device in the visual wavelength range such as organic EL. In addition, there is a problem in that impurities cannot be mixed during device fabrication because vacuum deposition cannot be performed due to low decomposition temperature or high molecular weight, and the complex is decomposed during deposition.

JP-A-8-239655 Japanese Patent Laid-Open No. 7-183561 JP-A-3-200289 US Pat. No. 6,097,147 International Publication WO01 / 41512 US2001 / 0025108 Publication US2002 / 0182441 Publication JP 2002-170684 A JP 2003-123982 A JP 2003-133074 A International Publication No. WO05 / 019373 D. F. OBryen and M.M. A. Baldo et al "Improved energy transfer electrophoretic devices" Vol. 74 No. 3, pp 442-444, January 18, 1999 M.M. A. Baldo et al "Very high-efficiency green organic light-emitting devices based on electrophoretics" Applied Physics letters Vol. 75 No. 1, pp4-6, July 5, 1999 Chem. Rev. 2000, 100, p39 J. et al. Am. Chem. Soc. 1991, 113, p361 Angew. Chem. Int. Ed. , 2002, 41, p1290 J. et al. Am. Chem. Soc. 1999, 121, p2674. Organometallics, 1999, 18, p2370 Angew. Chem. Int. Ed. , 2002, 41, p 1363 Angew. Chem. Int. Ed. , 2002, 41, p1745 Organometallics, 2000, 19, p3659 TetrahedronAymmetry, 2003, 14, p951 J. et al. Organomet. Chem. , 1982, 239, C26-C30. Chem. Commun. , 2002, p2518

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an organic EL device that emits blue light with high luminous efficiency and a novel transition metal complex compound that realizes the organic EL device.

  As a result of intensive studies to achieve the above object, the present inventors have made the complex ligand a tridentate ligand type having a carbene bond in a transition metal complex compound having a metal carbene bond. Thus, it was found that the emission wavelength can be increased as compared with a bidentate complex having a carbene bond. This phenomenon is useful as a technique capable of adjusting the emission wavelength to a desired one, and is particularly useful in leading a material having an emission wavelength in the ultraviolet region to a material having emission in the blue region (enlarging the visual wavelength region). be able to). It has been found that by using this technology, an organic EL element having high luminous efficiency and blue light emission can be obtained, and the present invention has been completed.

That is, the present invention provides a transition metal complex compound having a metal carbene bond represented by the following general formula (1).

[In the general formula (1), a bond indicated by a solid line (−) indicates a covalent bond, and a bond indicated by an arrow (→) indicates a coordinate bond. L ¹ -L ² -L ³ and L ⁴ -L ⁵ -L ⁶ represent bridged tridentate ligands.
L ² is a trivalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms that may have a substituent, a trivalent heterocyclic group having 3 to 30 nuclear atoms that may have a substituent, A C1-C30 trivalent carboxyl-containing group which may have a substituent, a trivalent amino group which may have a substituent or a hydroxyl group-containing hydrocarbon group, and a substituent which may have 3 A trivalent carbon atom having 3 to 50 carbon atoms, an optionally substituted trivalent alkane residue having 1 to 30 carbon atoms, and an optionally substituted trivalent carbon atom having 2 to 2 carbon atoms. 30 alkene residue, a trivalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent,
L ⁶ is a divalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms that may have a substituent, a divalent heterocyclic group having 3 to 30 nuclear atoms that may have a substituent, A C1-C30 divalent carboxyl-containing group that may have a substituent, a trivalent amino group or a hydroxyl group-containing hydrocarbon group that may have a substituent, or a substituent that may have 2 A C3-C50 cycloalkane residue having a valent nucleus, a divalent C1-C30 alkane residue which may have a substituent, and a divalent C2 having 2 substituents which may have a substituent 30 alkene residue, a divalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent,
L ¹ , L ³ and L ⁴ are each independently a monovalent group having a carbene carbon which may have a substituent, or a monovalent fragrance having 6 to 30 nuclear carbon atoms which may have a substituent. An aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 30 nuclear atoms, which may have a substituent,
L ⁵ is a divalent group having a carbene carbon which may have a substituent, a divalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms which may have a substituent, or a substituent. A divalent heterocyclic group having 3 to 30 nuclear atoms,
At least one of L ¹ , L ³ , L ⁴ and L ⁵ has an optionally substituted carbene carbon,
X represents a conjugate base of an acidic compound having an acid dissociation constant (pKa value) of 15 or less,
n is an integer of 0 to 2, and when n is 2, each of L ¹ , L ² and L ³ may be the same or different. When n is 0, each of L ⁴ , L ⁵ and L ⁶ is It can be the same or different. ]

  Further, the present invention provides an organic EL device in which an organic thin film layer composed of one or more layers having at least a light emitting layer is sandwiched between an anode and a cathode, wherein at least one layer of the organic thin film layer is the transition metal complex compound The organic EL element containing this is provided.

  The organic EL device using the transition metal complex compound having a metal carbene bond of the present invention has high luminous efficiency and emits blue light.

The transition metal complex compound of the present invention is a transition metal complex compound having a metal carbene bond represented by the following general formula (1).

In the general formula (1), a bond indicated by a solid line (−) indicates a covalent bond, and a bond indicated by an arrow (→) indicates a coordinate bond. L ¹ -L ² -L ³ and L ⁴ -L ⁵ -L ⁶ represent bridged tridentate ligands.
In general (1), L ² is a trivalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms which may have a substituent, and 3 to 30 nuclear atoms which may have a substituent. Trivalent heterocyclic group, C1-C30 trivalent carboxyl-containing group which may have a substituent, Trivalent amino group or hydroxyl group-containing hydrocarbon group which may have a substituent, Substituent May have a trivalent nuclear cycloalkane residue having 3 to 50 carbon atoms, an optionally substituted trivalent alkane residue having 1 to 30 carbon atoms, and may have a substituent. A trivalent alkene residue having 2 to 30 carbon atoms and a trivalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent.

As the aromatic hydrocarbon group, those having 6 to 18 nuclear carbon atoms are preferable, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2- Yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p- Ryl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4 '-Methylbiphenylyl group, 4 "-t-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylylenyl group, 3,4- Examples of the trivalent group include a xylylenyl group, a 2,5-xylylenyl group, a mesityrenyl group, and a perfluorophenyl group.
Among these, preferably, phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-tolyl group, 3, The 4-xylylenyl group is a trivalent group.

The heterocyclic group is preferably one having 3 to 18 nuclear atoms, such as 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 1-imidazolyl group, 2- Imidazolyl group, 1-pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazo [1,5 -A] pyridinyl group, 1-imidazo [4,5-a] pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5 -Indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4 Isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6- Benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7- Isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxa Nyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, β-carbolin-1-yl, β-carboline- 3-yl, β-carbolin-4-yl, β-carbolin-5-yl, β-carbolin-6-yl, β-carbolin-7-yl, β-carbolin-8-yl, β-carboline-9- Yl, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group Group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group, 1,7-phenanthrolin-4-yl group, 1,7- Phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl group, 1, 7-phenanthrolin-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthrolin-9-yl Group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2- Yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group, 1,9-phenanthroline- 6-yl group, 1,9-phenanthroline-7-yl group, 1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group, 1,10-phenance Lorin-2-yl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9- Phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2, 9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group, 2 9-phenanthroline-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl Group, 2,8-phenanthroline-9-yl group, 2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3 -Yl group, 2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthroline -8-yl group, 2,7-phenanthrolin-9-yl group, 2,7-phenance Rin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group Group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-flazanyl Group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl Group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrole Roll-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1- Indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, Examples of the trivalent group include 2-t-butyl 3-indolyl group, 4-t-butyl 3-indolyl group, pyrrolidine, pyrazolidine, piperidine and the like.
Among these, 2-pyridinyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazo [1,5-a] pyridinyl group, 1-imidazo [4,5-a] pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4- Indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7- Isoindolyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl Group, in which the trivalent group of the 9-carbazolyl group.

Examples of the carboxyl-containing group include those having a trivalent group such as an ester bond (—C (═O) O—), a methyl ester, an ethyl ester, and a butyl ester.
Examples of the cycloalkane residue include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norbornyl group. A trivalent group is exemplified.

The alkane residue is preferably one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl Group, 3-methylpentyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1, -Dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1- Cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl Group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 1,2-dinitroethyl group, 2,3-dinitro-t-butyl group, 1,2, - trinitro propyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, those with trivalent group 3,5-tetramethyl cyclohexyl group.
Of these, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, and n-heptyl are preferred. Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group Group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclohexyl group This is a trivalent group.

  The alkene residue is preferably one having 2 to 16 carbon atoms, for example, vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methyl. Vinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl Group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group, 3-phenyl-1-butenyl group and the like, and these as divalent groups Preferably, styryl group, 2,2-diphenylvinyl group, and 1,2-diphenylvinyl group are trivalent groups.

The arylalkane residue is preferably one having 7 to 18 carbon atoms, for example, benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t. -Butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1- β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group M-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p Bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl Group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, Examples include trivalent groups such as o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like.
Among these, benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl are preferable. The group is a trivalent group.
Examples of the amino group or hydroxyl group-containing hydrocarbon group include an amino group having each hydrocarbon group represented by L ² and a group in which a hydrogen atom of the hydrocarbon group is replaced with a hydroxyl group.

In general (1), L ⁶ is a divalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms which may have a substituent, and 3 to 30 nuclear atoms which may have a substituent. A divalent heterocyclic group, a C1-C30 divalent carboxyl-containing group which may have a substituent, a trivalent amino group or a hydroxyl group-containing hydrocarbon group which may have a substituent, a substituent May have a divalent nucleus having 3 to 50 carbon atoms, a divalent alkane residue having 1 to 30 carbon atoms which may have a substituent, and a substituent. A divalent alkene residue having 2 to 30 carbon atoms and a divalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent.
Specific examples of these groups include those in which the specific examples of L ² are divalent groups, and preferable examples are the same.

In general (1), L ¹ , L ³ and L ⁴ are each independently a monovalent group having a carbene carbon which may have a substituent, or a nuclear carbon number which may have a substituent 6 Or a monovalent aromatic hydrocarbon group having 3 to 30 nuclear atoms, which may have a substituent.
Examples of the monovalent group having L ¹ , L ³ and L ⁴ carbene carbons include cyclic diarylcarbene, cyclic diaminocarbene, cyclic aminooxycarbene, cyclic aminothiocarbene, and cyclic diborylcarbene. Reference Chem. Rev. 2000, 100, p39).
More specifically, (imidazolyl-2-ylidene, N ¹ ) having a substituent at N at the 3-position, (1,2,4-triazolyl-5-ylidene, N having a substituent at N at the 4-position ¹ ) group, (thiazolyl-2-ylidene, N) group, (4,5-benzimidazolyl-2-ylidene, N ¹ ) group having a substituent at N at position 3, (imidazo [1,5a] pyridyl-3 -Iridene, N ² ) group and the like.
Among these, a (imidazolyl-2-ylidene, N ¹ ) group having a substituent at N at the 3-position, a (4,5-benzoimidazolyl-2-ylidene, N ¹ ) group having a substituent at N at the 3-position, (Imidazo [1,5a] pyridyl-3-ylidene, N ² ) group is preferred, and (imidazolyl-2-ylidene, N ¹ ) group having a substituent at N at position 3 has a substituent at N at position 3 (4,5-Benzimidazolyl-2-ylidene, N ¹ ) group is more preferred.

Among these, preferable structures are as follows. In the following, Ph is a phenyl group, Me is a methyl group, and Et is an ethyl group.

Examples of the aromatic hydrocarbon group and heterocyclic group of L ¹ , L ³ and L ⁴ include the same monovalent examples as those described above for L ² .
In general (1), L ⁵ is a divalent group having a carbene carbon which may have a substituent, or a divalent aromatic hydrocarbon having 6 to 30 nuclear carbon atoms which may have a substituent. A divalent heterocyclic group having 3 to 30 nuclear atoms which may have a group or a substituent, and examples of these groups include divalent examples of L ¹ , L ³ and L ⁴ . And the like.
In general (1), at least one of L ¹ , L ³ , L ⁴ and L ⁵ has a carbene carbon which may have a substituent.

In general (1), X has an acid dissociation constant (pKa value) of 15 or less (preferably,
−5 or less) is a conjugate base of an acidic compound.
Examples of such a conjugate base include super strong acids, carboxylic acids, aldehydes, ketones, alcohols, thioalcohols, phenols, amines, amides, aromatics having a pKa value of −10 or less. Conjugated bases or halide ions of
Conjugated bases or halide ions of super strong acids are preferred.
As the conjugate base of super strong acids having a pKa value of −10 or less, SbF ₆ ⁻ , FSO ₃ ⁻ , ClO ₄ ⁻ , I ⁻ , TfO ⁻ , Tf ₂ N ⁻ (Tf− is CF ₃ SO ₂ −) , PF ₆ ⁻ , BF ₄ ⁻ , [Ar ₄ B] ^{− and the} like are conjugated bases of carboxylic acids such as RCOO ⁻ and ArCOO ^{− and the} like, and conjugated bases of aldehydes such as R ⁻ COH and the like are conjugates of ketones. As the base, R—COR ′ and the like, as the conjugate base of alcohols, RO ^{− and the} like, as the conjugate base of thioalcohols, RSO ^{− and the} like, as the conjugate base of phenols, ArO 2 ⁻ etc. aromatic group), the conjugate base of amines RR'N ^-. Examples of the conjugate base of amides RR'NCOR '' ^- and the like (the R, R ', R''is a hydrocarbon group), Aromatic conjugate bases include (substituted) cyclopentadienyl anio Etc., and examples of the halide ion ^{F -, Cl -, Br -} , I - , and the like.
In general (1), n is an integer of 0 to 2, and when n is 2, each of L ¹ , L ² and L ³ may be the same or different, and when n is 0, each L ⁴ , L ⁵ and L ⁶ may be the same or different.

In general (1), the following structures are preferred as specific examples of the L ¹ L ² L ³ Ir part and the L ⁴ L ⁵ L ⁶ Ir part. In the following structure, M is Ir.

［一般的（２）において、Ｌ¹、Ｌ²、Ｌ³及びＸは前記と同じである。］ Moreover, it is preferable that the transition metal compound represented by the general formula (1) has a structure represented by the following general formula (2).

[In General (2), L ¹ , L ² , L ³ and X are the same as described above. ]

Furthermore, the transition metal compound represented by the general formula (1) is preferably a structure represented by the following general formula (3).

In General Formula (3), R ^{1 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a thiocyano group, a cyano group, a nitro group, a —S (═O) ₂ R ′ group, or —S (= O) R ′, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 30 carbon atoms, and an optionally substituted nucleus An aromatic hydrocarbon group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 nuclear carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, and a substituent An alkenyl group having 2 to 30 carbon atoms, a heterocyclic group having 3 to 30 nuclear atoms that may have a substituent, and an alkoxy group having 1 to 30 carbon atoms that may have a substituent An aryloxy group having 6-30 nuclear carbon atoms that may have a substituent, and an aryloxy group having 3-30 nuclear atoms that may have a substituent. An alkylamino group having 6 to 30 carbon atoms that may have a substituent, an alkylamino group having 3 to 30 nuclear atoms that may have a substituent, and a carbon number that may have a substituent It is a 6-30 arylsilyl group and a C1-C30 carboxyl-containing group, and may be crosslinked.
(R ′ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 30 carbon atoms, or a substituent. An aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms, a cycloalkyl group having 3 to 50 nuclear carbon atoms that may have a substituent, and 7 to 7 carbon atoms that may have a substituent. 40 aralkyl groups, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted heterocyclic group having 3 to 30 nuclear atoms, and an optionally substituted carbon An alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 nuclear carbon atoms which may have a substituent, an alkylamino group having 3 to 30 carbon atoms which may have a substituent, and a substituent; An arylamino group having 6 to 30 carbon atoms which may be substituted, and an alkylsilyl group having 3 to 30 carbon atoms which may have a substituent And an arylsilyl group having 6 to 30 carbon atoms which may have a substituent, and a carboxyl-containing group having 1 to 30 carbon atoms which may have a substituent.)

As said alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group , 3-methylpentyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2 Dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl Group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group Nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 1,2-dinitroethyl group, 2,3-dinitro-t-butyl group, 1,2,3 Trinitro propyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, 3,5-tetramethyl cyclohexyl group.
Of these, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, and n-heptyl are preferred. Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group Group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclohexyl group is there.

The halogenated alkyl group is preferably one having 1 to 10 carbon atoms, for example, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1, 3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2- Dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodo Isobutyl, 1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-t-butyl, 1,2,3-to Iodopropyl group, fluoromethyl group, 1-fluoromethyl group, 2-fluoromethyl group, 2-fluoroisobutyl group, 1,2-difluoroethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, perfluoroisopropyl Group, perfluorobutyl group, perfluorocyclohexyl group and the like.
Among these, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, and a perfluorocyclohexyl group are preferable.

As the aromatic hydrocarbon group, those having 6 to 18 nuclear carbon atoms are preferable, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2- Yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p- Ryl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4 '-Methylbiphenylyl group, 4 "-t-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylylenyl group, 3,4- Examples include a xylylenyl group, a 2,5-xylylenyl group, a mesityrenyl group, and a perfluorophenyl group.
Among these, preferably, phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-tolyl group, 3, 4-Xylylenyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norbornyl group. It is done.
The aralkyl group is preferably one having 7 to 18 carbon atoms, for example, benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl. Group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β- Naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m -Methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromo Benzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group P-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o -Cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like, preferably benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyano Benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenyl Isopropyl group.

  The alkenyl group is preferably one having 2 to 16 carbon atoms, for example, vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl. Group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group , 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group, 3-phenyl-1-butenyl group, etc., preferably styryl group, 2,2-diphenylvinyl group and 1,2-diphenylvinyl group.

The heterocyclic group is preferably one having 3 to 18 nuclear atoms, such as 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 1-imidazolyl group, 2- Imidazolyl group, 1-pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazo [1,5 -A] pyridinyl group, 1-imidazo [4,5-a] pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5 -Indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4 Isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6- Benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7- Isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxa Nyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, β-carbolin-1-yl, β-carboline- 3-yl, β-carbolin-4-yl, β-carbolin-5-yl, β-carbolin-6-yl, β-carbolin-7-yl, β-carbolin-6-yl, β-carboline-9- Yl, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group Group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group, 1,7-phenanthrolin-4-yl group, 1,7- Phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl group, 1, 7-phenanthrolin-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthrolin-9-yl Group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2- Yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group, 1,9-phenanthroline- 6-yl group, 1,9-phenanthroline-7-yl group, 1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group, 1,10-phenance Lorin-2-yl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9- Phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2, 9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group, 2 9-phenanthroline-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl Group, 2,8-phenanthroline-9-yl group, 2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3 -Yl group, 2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthroline -8-yl group, 2,7-phenanthrolin-9-yl group, 2,7-phenance Rin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group Group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-flazanyl Group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl Group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrole Roll-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1- Indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, Examples include 2-t-butyl 3-indolyl group, 4-t-butyl 3-indolyl group, pyrrolidine, pyrazolidine, piperidine and the like.
Among these, 2-pyridinyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazo [1,5-a] pyridinyl group, 1-imidazo [4,5-a] pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4- Indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7- Isoindolyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl Group, a 9-carbazolyl group.

The alkoxy group and aryloxy group are groups represented by —OX ¹ , and examples of X ¹ include the same examples as those described for the alkyl group, halogenated alkyl group, and aryl group.
The alkylamino group and arylamino group are groups represented by —NX ¹ X ² , and examples of X ¹ and X ² include those described for the alkyl group, halogenated alkyl group, and aryl group, respectively. Similar examples are given.
Examples of the carboxyl-containing group include methyl ester, ethyl ester, and butyl ester.
Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, and a propyldimethylsilyl group.
Examples of the arylsilyl group include a triphenylsilyl group, a phenyldimethylsilyl group, a t-butyldiphenylsilyl group, and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the ring structure formed by crosslinking of R ^{1 to} R ⁹ include the same examples as those given for the heterocyclic group.

Examples of the substituent of each group in the general formulas (1) to (3) include a substituted or unsubstituted aryl group having 5 to 50 nuclear carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted group. An unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear carbon atoms, a substituted or unsubstituted nuclear carbon Examples thereof include an arylthio group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, an amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a carboxyl group.
Among these, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms are preferable, an alkyl group having 1 to 6 carbon atoms, and a cyclohexane having 5 to 7 carbon atoms. Alkyl groups are more preferred, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group. Is particularly preferred.

ＣＯＤは、１，５−シクロオクタジエンである。 Next, as a manufacturing method of the transition metal complex compound of this invention, the following synthetic route etc. are mentioned, for example.
<Synthesis route 1>

COD is 1,5-cyclooctadiene.

<Synthetic route 2>

The organic EL device of the present invention is an organic EL device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes comprising an anode and a cathode, and at least one of the organic thin film layers Contains a metal complex compound represented by the general formula (1) of the present invention.
As content of the transition metal complex compound of this invention in the said organic thin film layer, it is 0.1-100 weight% normally with respect to the mass of the whole light emitting layer, and it is preferable in it being 1-30 weight%.
In the organic EL device of the present invention, the light emitting layer preferably contains the transition metal complex compound of the present invention as a light emitting material or a dopant. Moreover, although the said light emitting layer is normally thinned by vacuum evaporation or application | coating, since the manufacturing process can be simplified more by application | coating, when the layer containing the transition metal complex compound of this invention is formed into a film by application | coating. preferable.
In the organic EL device of the present invention, when the organic thin film layer is a single layer type, the organic thin film layer is a light emitting layer, and this light emitting layer contains the transition metal complex compound of the present invention. In addition, multilayer organic EL elements include (anode / hole injection layer (hole transport layer) / light emitting layer / cathode), (anode / light emitting layer / electron injection layer (electron transport layer) / cathode), ( Anode / hole injection layer (hole transport layer) / light emitting layer / electron injection layer (electron transport layer) / cathode) and the like.

  The anode of the organic EL device of the present invention supplies holes to a hole injection layer, a hole transport layer, a light emitting layer and the like, and it is effective to have a work function of 4.5 eV or more. As a material for the anode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples of the material of the anode include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, nickel, and these conductive metals. Preferred examples include a mixture or laminate of oxide and metal, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, and laminates of these with ITO. Is a conductive metal oxide, and in particular, ITO is preferably used from the viewpoint of productivity, high conductivity, transparency, and the like. The film thickness of the anode can be appropriately selected depending on the material.

  The cathode of the organic EL device of the present invention supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like. As a material of the cathode, metal, alloy, metal halide, metal oxide, electric conduction Or a mixture of these can be used. Specific examples of cathode materials include alkali metals (eg, Li, Na, K, etc.) and their fluorides or oxides, alkaline earth metals (eg, Mg, Ca, etc.) and their fluorides or oxides, gold Silver, lead, aluminum, sodium-potassium alloy or sodium-potassium mixed metal, lithium-aluminum alloy or lithium-aluminum mixed metal, magnesium-silver alloy or magnesium-silver mixed metal, or rare earth metals such as indium and ytterbium, etc. Can be mentioned. Among these, aluminum, lithium-aluminum alloy or lithium-aluminum mixed metal, magnesium-silver alloy or magnesium-silver mixed metal are preferable. The cathode may have a single layer structure of the material or a laminated structure of layers containing the material. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide is preferable. The film thickness of the cathode can be appropriately selected depending on the material.

  The hole injection layer and the hole transport layer of the organic EL device of the present invention have any one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. If it is what. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples include copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organosilane derivatives, and transition metal complex compounds of the present invention. Further, the hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. May be.

  The electron injection layer and the electron transport layer of the organic EL device of the present invention have any one of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode. If it is. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives. , Represented by metal complexes of aromatic ring tetracarboxylic anhydrides such as distyrylpyrazine derivatives, naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Examples include various metal complexes, organosilane derivatives, and transition metal complex compounds of the present invention. Further, the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

Further, examples of the electron transport material used for the electron injection layer and the electron transport layer include the following compounds.

In the organic EL device of the present invention, it is preferable that the electron injection layer and / or the electron transport layer contain a π electron deficient nitrogen-containing heterocyclic derivative as a main component.
As the π-electron deficient nitrogen-containing heterocyclic derivative, a nitrogen-containing 5-membered ring derivative selected from a benzimidazole ring, a benztriazole ring, a pyridinoimidazole ring, a pyrimidinoimidazole ring, and a pyridazinoimidazole ring, pyridine Preferred examples include nitrogen-containing 6-membered ring derivatives composed of a ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Preferred examples of the nitrogen-containing 5-membered ring derivative include structures represented by the following general formula B-I. Preferred examples of the nitrogen-containing 6-membered ring derivative include structures represented by the following general formulas C-I, C-II, C-III, C-IV, CV and C-VI, particularly preferably It is a structure represented by general formulas C-I and C-II.

一般式（Ｂ−Ｉ）において、Ｌ^Bは二価以上の連結基を表し、好ましくは、炭素、ケイ素、窒素、ホウ素、酸素、硫黄、金属、金属イオンなどで形成される連結基であり、より好ましくは炭素原子、窒素原子、ケイ素原子、ホウ素原子、酸素原子、硫黄原子、芳香族炭化水素環、芳香族へテロ環であり、さらに好ましくは炭素原子、ケイ素原子、芳香族炭化水素環、芳香族へテロ環である。

In the general formula ^(B-I), L B represents a divalent or higher linking group, preferably, the linking group formed of carbon, silicon, nitrogen, boron, oxygen, sulfur, metals, etc. with metal ions, More preferably a carbon atom, a nitrogen atom, a silicon atom, a boron atom, an oxygen atom, a sulfur atom, an aromatic hydrocarbon ring, an aromatic heterocycle, and still more preferably a carbon atom, a silicon atom, an aromatic hydrocarbon ring, An aromatic heterocycle.

L ^B may have a substituent, preferably an alkyl group as a substituent, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, aromatic hetero complex A cyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, or an aromatic heterocyclic group, and still more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group. An aromatic heterocyclic group Particularly preferably an alkyl group, an aryl group, an alkoxy group, an aromatic heterocyclic group.

Specific examples of the linking group represented by L ^B may include the following.

In the general formula (BI), X ^B2 represents —O—, —S— or ═N—R ^B2 . R ^B2 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group.
The aliphatic hydrocarbon group represented by R ^B2 is a linear, branched or cyclic alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms). And examples thereof include methyl, ethyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and an alkenyl group (preferably having 2 to 2 carbon atoms). 20, more preferably an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.), An alkynyl group (Preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a propargyl group, 3 Pentynyl group and the like.), More preferably an alkyl group.
The aryl group represented by R ^B2 is a monocyclic or condensed ring aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, For example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-trifluoromethylphenyl, pentafluorophenyl, 1-naphthyl, 2-naphthyl and the like can be mentioned.

The heterocyclic group represented by R ^B2 is a monocyclic or condensed heterocyclic group (preferably a heterocyclic group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 2 to 10 carbon atoms). Yes, preferably an aromatic heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom, such as pyrrolidine, piperidine, piperazine, morpholine, thiophene, selenophene, furan, pyrrole, imidazole , Pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteri , Acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene, carbazole, azepine, etc., preferably furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine Quinoline, phthalazine, naphthyridine, quinoxaline and quinazoline, more preferably furan, thiophene, pyridine and quinoline, and still more preferably quinoline.
The aliphatic hydrocarbon group, aryl group, and heterocyclic group represented by R ^B2 may have a substituent, and examples thereof include the same as L ^B described above.
R ^B2 is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably an aryl group or an aromatic heterocyclic group, and still more preferably an aryl group.

X ^B2 is preferably —O—, ═N—R ^B2 , more preferably ═N—R ^B2 , and particularly preferably ═N—Ar ^B2 (Ar ^B2 is an aryl group (preferably having 6 carbon atoms). To 30, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon aryl groups, and aromatic heterocyclic groups (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably). Is an aromatic heterocyclic group having 2 to 10 carbon atoms, preferably an aryl group).

Z ^B2 represents an atomic group necessary for forming an aromatic ring. The aromatic ring formed by Z ^B2 may be either an aromatic hydrocarbon ring or an aromatic heterocycle. Specific examples include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, and a pyrrole. Ring, furan ring, thiophene ring, selenophene ring, tellurophen ring, imidazole ring, thiazole ring, selenazole ring, tellurazole ring, thiadiazole ring, oxadiazole ring, pyrazole ring, etc., preferably benzene ring, pyridine ring, pyrazine A ring, a pyrimidine ring and a pyridazine ring, more preferably a benzene ring, a pyridine ring and a pyrazine ring, still more preferably a benzene ring and a pyridine ring, and particularly preferably a pyridine ring. The aromatic ring formed by ZB2 may further form a condensed ring with another ring, and may have a substituent. As a substituent, preferably an alkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, An aryloxy group, a halogen atom, a cyano group and a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an aromatic heterocyclic group, particularly preferably an alkyl group, an aryl group, Al Alkoxy group, an aromatic heterocyclic group.
n ^B2 is an integer of 1 to 4, preferably 2 to 3.

Of the compounds represented by the general formula (BI), more preferred is a compound represented by the following general formula (B-II).

In general formula (B-II), R ^B71 , R ^B72 and R ^B73 have the same ^{meanings as} R ^B2 in general formula ( ^BI ), respectively, and the preferred ranges are also the same.
Z ^B71 , Z ^B72 and Z ^B73 are the same as Z ^B2 in formula ( ^BI ), respectively, and the preferred ranges are also the same.
L ^B71 , L ^B72 and L ^B73 each represent a linking group, and examples thereof include a divalent example of L ^{B in} the general formula (BI), preferably a single bond or a divalent aromatic carbonization. A linking group composed of a hydrogen ring group, a divalent aromatic heterocyclic group, and a combination thereof, more preferably a single bond. L ^B71 , L ^B72 and L ^B73 may have a substituent, and examples of the substituent include those similar to L ^{B in the} general formula (BI).
Y represents a nitrogen atom, a 1,3,5-benzenetriyl group or a 2,4,6-triazinetriyl group. The 1,3,5-benzenetriyl group may have a substituent at the 2,4,6-position, and examples of the substituent include an alkyl group, an aromatic hydrocarbon ring group, and a halogen atom. It is done.

Specific examples of the nitrogen-containing 5-membered ring derivative represented by the general formula (BI) or (B-II) are shown below, but are not limited to these exemplified compounds.

(Cz-) nA (CI)
Cz (-A) m (C-II)
[Wherein, Cz is a substituted or unsubstituted carbazolyl group, arylcarbazolyl group or carbazolylalkylene group, and A is a group formed from a site represented by the following general formula (A).
n and m are integers of 1 to 3, respectively.
(M) p- (L) q- (M ′) r (A)
(M and M ′ are each independently a nitrogen-containing heteroaromatic ring having 2 to 40 carbon atoms to form a ring, and the ring may or may not have a substituent. M and M ′ may be the same or different, L is a single bond, an arylene group having 6 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or a heteroaromatic ring having 2 to 30 carbon atoms. , May or may not have a substituent bonded to the ring, p is 0 to 2, q is 1 to 2, and r is an integer of 0 to 2. However, p + r is 1 or more. is there.)]

また、一般式（Ａ）で表される基の結合様式は、パラメータｐ，ｑ，ｒの数により、具体的には以下の表中(1)から(16)に記載された形である。 The bonding mode of the general formulas (CI) and (C-II) is specifically represented by the number of parameters n and m as shown in the following table.

Further, the bonding mode of the group represented by the general formula (A) is specifically the form described in (1) to (16) in the following table depending on the number of parameters p, q and r.

  In the general formulas (CI) and (C-II), when Cz is bonded to A, it may be bonded to any part of M, L, M ′ representing A. For example, in Cz-A where m = n = 1, when p = q = r = 1 ((6) in the table), A becomes M-L-M 'and Cz-M-L-M', M- L (-Cz) -M 'and ML-M'-Cz are represented as three bonding modes. Similarly, for example, in Cz-A-Cz where n = 2 in the general formula (CI), in the case of p = q = 1, r = 2 ((7) in the table), A is M-LM It becomes '-M' or ML (-M ')-M' and is represented as the following binding mode.

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

（式中、Ａｒ₁₁〜Ａｒ₁₃は、それぞれ一般式（Ｂ−Ｉ）のＲ^B2と同様の基を示し、具体例も同様であり、Ａｒ₁〜Ａｒ₃は、一般式（Ｂ−Ｉ）のＲ^B2と同様の基を２価にしたものを示し、具体例も同様である。）

(In the formula, Ar _{11 to} Ar ₁₃ each represent the same group as R ^{B2 in the} general formula (BI), and specific examples thereof are also the same. Ar _{1 to} Ar ₃ are the same in the general formula (BI)). the same groups as R ^B2 in indicates those divalent, examples versa.)

Although the specific example of general formula (C-III) is shown below, it is not limited to this.

（式中、Ｒ₅₉〜Ｒ₆₂は、それぞれ一般式（Ｂ−Ｉ）のＲ^B2と同様の基を示し、具体例も同様である。）

(In the formula, R _{59 to} R ₆₂ each represent the same group as R ^{B2 in} formula (BI), and specific examples thereof are also the same).

Although the specific example of general formula (C-IV) is shown below, it is not limited to these.

（式中、Ａｒ₄〜Ａｒ₆は、それぞれ一般式（Ｂ−Ｉ）のＲ^B2と同様の基を示し、具体例も同様である。）

(In formula, Ar < ₄ > -Ar < ₆ > respectively shows the group similar to R ^<B2 > of general formula (BI), and a specific example is also the same.)

Although the specific example of general formula (CV) is shown below, it is not limited to this.

（式中、Ａｒ₇〜Ａｒ₁₀は、それぞれ一般式（Ｂ−Ｉ）のＲ^B2と同様の基を示し、具体例も同様である。）

(In formula, Ar < ₇ > -Ar < ₁₀ > shows the group similar to R ^<B2 > of general formula (BI) respectively, and a specific example is also the same.)

Although the specific example of general formula (C-VI) is shown below, it is not limited to this.

In the organic EL device of the present invention, it is preferable to use an insulator or a semiconductor inorganic compound as a substance constituting the electron injection / transport layer. If the electron injecting / transporting layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injecting property can be improved. As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injecting / transporting layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injecting property can be further improved.
Specifically, preferable alkali metal chalcogenides include, for example, Li ₂ O, Na ₂ S, Na ₂ Se and the like, and preferable alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS and CaSe is mentioned. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.

The semiconductor constituting the electron injecting / transporting layer includes at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. One kind or a combination of two or more kinds of oxides, nitrides, oxynitrides, and the like can be given. Moreover, it is preferable that the inorganic compound which comprises an electron carrying layer is a microcrystal or an amorphous insulating thin film. If the electron transport layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include the alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides described above.
Furthermore, in the organic EL device of the present invention, the electron injection layer and / or the electron transport layer may contain a reducing dopant having a work function of 2.9 eV or less. In the present invention, the reducing dopant is a compound that increases the electron injection efficiency.

  In the present invention, a reducing dopant is preferably added to the interface region between the cathode and the organic thin film layer, and at least a part of the organic layer contained in the interface region is reduced and anionized. Preferred reducing dopants include alkali metal, alkaline earth metal oxide, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal halide, rare earth metal oxidation. Or at least one compound selected from the group of rare earth metal halides, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes. More specifically, preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1.95 eV). ) And at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV). Examples include at least one alkaline earth metal selected from the group, and a work function of 2.9 eV is particularly preferable. Among these, a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the light emission luminance and extend the life of the organic EL element.

Examples of the alkaline earth metal oxide include BaO, SrO, CaO and Ba _x Sr _1-x O (0 <x <1) mixed with these, Ba _x Ca _1-x O (0 <x < 1) can be mentioned as a preferable one. Examples of the alkali oxide or alkali fluoride include LiF, Li ₂ O, and NaF. The alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as they contain at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions as metal ions. Examples of the ligand include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzo Examples include, but are not limited to, triazole, hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines, and derivatives thereof.

Moreover, as a preferable form of a reducing dopant, it forms in a layer form or an island form. A preferable film thickness when used in a layered form is 0.05 to 8 nm.
As a method for forming an electron injecting / transporting layer containing a reducing dopant, a reducing dopant is deposited by resistance heating vapor deposition, and an organic substance that is a light-emitting material or an electron injecting material that forms an interface region is deposited at the same time. A method in which a reducing dopant is dispersed in is preferable. The dispersion concentration is 100: 1 to 1: 100, preferably 5: 1 to 1: 5, as a molar ratio. When forming the reducing dopant in layers, after forming the light emitting material or electron injecting material, which is an organic layer at the interface, into layers, the reducing dopant is vapor-deposited by a resistance heating vapor deposition method. Formed at 5 nm to 15 nm. When forming the reducing dopant in an island shape, after forming the light emitting material or electron injecting material which is the organic layer at the interface, the reducing dopant is vapor-deposited by resistance heating vapor deposition method alone, preferably 0.05 Form at ˜1 nm.

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

In the organic EL device of the present invention, the method for forming each layer is not particularly limited, but a vacuum deposition method, an LB method, a resistance heating deposition method, an electron beam method, a sputtering method, a molecular lamination method, a coating method. Various methods such as a spin coating method, a casting method, a dip coating method, an ink jet method, and a printing method can be used. In the present invention, a coating method that is a coating method is preferable.
In addition, the organic thin film layer containing the metal complex compound of the present invention can be prepared by vacuum deposition, molecular beam deposition (MBE), or solution dipping in a solvent, spin coating, casting, bar coating, roll It can be formed by a known method such as a coating method.
In the coating method, the metal complex compound of the present invention can be dissolved in a solvent to prepare a coating solution, and the coating solution can be applied on a desired layer (or electrode) and dried. The coating solution may contain a resin, and the resin can be dissolved in a solvent or dispersed. As the resin, a non-conjugated polymer (for example, polyvinyl carbazole) or a conjugated polymer (for example, a polyolefin-based polymer) can be used. More specifically, for example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin. , Polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicon resin and the like.
In addition, the thickness of each organic layer of the organic EL element of the present invention is not particularly limited, but in general, if the film thickness is too thin, defects such as pinholes are likely to occur. Conversely, if it is too thick, a high applied voltage is required and efficiency is increased. Usually, the range of several nm to 1 μm is preferable because of deterioration.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by these.
Example 1 (Synthesis of [Ir (NHC) ₂ ] PF ₆ )
[Ir (NHC) ₂ ] PF ₆ was synthesized by the following route.

[Ir (COD) Cl] ₂ (0.168 g, 0.25 mmol, COD is 1,5-cyclooctadiene), NaOMe (0.106 g, 2.00 mmol), and pre-degassed 2-ethoxy Ethanol (25 ml) was placed in a Schlenk flask and reacted at room temperature for 2 hours (the reaction solution changed from orange to green). Next, the above [(NHC) ₂ ] I ₂ (0.496 g, 1.00 mmol) was added and reacted at 130 ° C. for 3 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure to obtain a brown oil. Next, when methylene chloride was added, a brown solid precipitated, and this solid was removed by filtration. The filtrate was concentrated, and the yellow intermediate product was separated and purified by silica gel flash chromatography (solvent: methylene chloride). Next, a methanol / water mixed solution (10/3 [volume ratio]) in which 0.5 g of KPF ₆ was dissolved was added to the obtained product, and the resulting yellow solid was purified by alumina chromatography (developing solvent: Methylene chloride / methanol 50/1 [volume ratio]). The solvent was distilled off to obtain 12.8 g (yield 3.1%) of the target compound as a yellow solid. From the following ¹ H-NMR and ESI-mass measured values, the product was identified.
¹ H-NMR (500 MHz, solvent: deuterated acetonitrile) 7.63 (d, 4H), 7.33 (d, 4H), 7.26 (t, 2H), 6.68 (d, 4H), 2. 39 (s, 12H)
ESI-mass (electrospray ionization mass spectrum) 667.1212 (calculated value 667.1887)
The quantum yield was 0.31 for the powder and 0.10 for the solution (methylene chloride).
The quantum efficiency was measured as follows.
<Measurement of quantum yield (powder)>
Apparatus: Quantum yield measuring apparatus C9920-01 manufactured by Hamamatsu Photonics Co., Ltd.
Method: Calculated as the ratio of the number of photons emitted by light emission to the number of photons absorbed by the material by the absolute method using an integrating sphere. Using a petri dish made of quartz, the sample (powder) was placed in an integrating sphere and measured.
<Measurement of quantum yield (solution)>
Apparatus: Quantum yield measuring apparatus C9920-01 manufactured by Hamamatsu Photonics Co., Ltd.
Method: Measurement with a solution was carried out using dichloromethane as a solvent, putting the solvent in a quartz cell, and adjusting the concentration so that the excitation wavelength (337 nm) was approximately halved (about 10 ⁻⁵ M).
Table 1 shows the results of measurement of the ultraviolet-visible light absorption spectrum and emission spectrum (in solution, room temperature and 77 K) of the obtained compound [Ir (NHC) ₂ ] PF ₆ .

Example 2 (Synthesis of [Ir (NHC) ₂ ] I)
[Ir (NHC) ₂ ] I was synthesized by the following route.

Compound A (0.56 g, 0.50 mmol), [(NHC) ₂ ] I ₂ (0.992 g, 2.00 mmol), and sodium carbonate (0.525 g, 5.00 mmol) under a nitrogen stream Was added to a 200 ml flask and reacted at 135 ° C. for 3 hours. After completion of the reaction, the reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure to obtain a brownish brown crude product. Next, the obtained crude product was purified by silica gel chromatography (developing solvent: methylene chloride / methanol 50/1 [volume ratio]). Further, it was purified again by silica gel chromatography in the same manner. This was recrystallized from a mixed solvent of acetonitrile / diethyl ether to obtain 8.51 mg (yield 1.1%) of the target compound as a yellow solid. It was identified as the target product from the following ¹ H-NMR measurement.
¹ H-NMR (500 MHz, solvent: deuterated acetonitrile) 7.56 (d, 4H), 7.27 (d, 4H), 7.18 (t, 2H), 6.61 (d, 4H), 2. 32 (s, 12H)
The quantum yield was 0.00 for powder and 0.38 for solution (methylene chloride).
FIG. 1 shows the result of X-ray crystal structure analysis (including acetone) of the obtained compound [Ir (NHC) ₂ ] I.
In addition, Table 1 shows the results of measurement of the ultraviolet-visible light absorption spectrum and emission spectrum (in solution, room temperature and 77 K) of the obtained compound [Ir (NHC) ₂ ] I.

2 is a diagram showing an X-ray crystal structure analysis of a transition metal complex compound obtained in Example 2. FIG.

Claims (8)

A transition metal complex compound having a metal carbene bond represented by the following general formula (1).

[In the general formula (1), a bond indicated by a solid line (−) indicates a covalent bond, and a bond indicated by an arrow (→) indicates a coordinate bond. L ¹ -L ² -L ³ and L ⁴ -L ⁵ -L ⁶ represent bridged tridentate ligands.
L ² is a trivalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms that may have a substituent, a trivalent heterocyclic group having 3 to 30 nuclear atoms that may have a substituent, A C1-C30 trivalent carboxyl-containing group which may have a substituent, a trivalent amino group which may have a substituent or a hydroxyl group-containing hydrocarbon group, and a substituent which may have 3 A trivalent carbon atom having 3 to 50 carbon atoms, an optionally substituted trivalent alkane residue having 1 to 30 carbon atoms, and an optionally substituted trivalent carbon atom having 2 to 2 carbon atoms. 30 alkene residue, a trivalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent,
L ⁶ is a divalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms that may have a substituent, a divalent heterocyclic group having 3 to 30 nuclear atoms that may have a substituent, A C1-C30 divalent carboxyl-containing group that may have a substituent, a trivalent amino group or a hydroxyl group-containing hydrocarbon group that may have a substituent, or a substituent that may have 2 A C3-C50 cycloalkane residue having a valent nucleus, a divalent C1-C30 alkane residue which may have a substituent, and a divalent C2 having 2 substituents which may have a substituent 30 alkene residue, a divalent arylalkane residue having 7 to 40 carbon atoms which may have a substituent,
L ¹ , L ³ and L ⁴ are each independently a monovalent group having a carbene carbon which may have a substituent, or a monovalent fragrance having 6 to 30 nuclear carbon atoms which may have a substituent. An aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 30 nuclear atoms, which may have a substituent,
L ⁵ is a divalent group having a carbene carbon which may have a substituent, a divalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms which may have a substituent, or a substituent. A divalent heterocyclic group having 3 to 30 nuclear atoms,
At least one of L ¹ , L ³ , L ⁴ and L ⁵ has an optionally substituted carbene carbon,
X represents a conjugate base of an acidic compound having an acid dissociation constant (pKa value) of 15 or less,
n is an integer of 0 to 2, and when n is 2, each of L ¹ , L ² and L ³ may be the same or different. When n is 0, each of L ⁴ , L ⁵ and L ⁶ is It can be the same or different. ] The transition metal complex compound having a metal carbene bond according to claim 1, which has a structure represented by the following general formula (2).

[In General (2), L ¹ , L ² , L ³ and X are the same as described above. ] The transition metal complex compound having a metal carbene bond according to claim 1, which has a structure represented by the following general formula (3).

[In General Formula (3), R ^{1 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a thiocyano group, a cyano group, a nitro group, a —S (═O) ₂ R ′ group, or —S ( ═O) R ′, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 30 carbon atoms, and optionally having a substituent. Aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms, cycloalkyl group having 3 to 30 nuclear carbon atoms which may have a substituent, aralkyl group having 7 to 40 carbon atoms which may have a substituent, substitution An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted heterocyclic group having 3 to 30 nuclear atoms, and an optionally substituted alkoxy having 1 to 30 carbon atoms Group, aryloxy group having 6-30 nuclear carbon atoms which may have a substituent, and 3-30 nuclear atoms optionally having a substituent An alkylamino group, an arylamino group having 6 to 30 carbon atoms which may have a substituent, an alkylsilyl group having 3 to 30 nuclear atoms which may have a substituent, and a carbon which may have a substituent These are an arylsilyl group having 6 to 30 carbon atoms and a carboxyl-containing group having 1 to 30 carbon atoms, and may be crosslinked.
(R ′ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 30 carbon atoms, or a substituent. An aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms, a cycloalkyl group having 3 to 50 nuclear carbon atoms that may have a substituent, and 7 to 7 carbon atoms that may have a substituent. 40 aralkyl groups, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted heterocyclic group having 3 to 30 nuclear atoms, and an optionally substituted carbon An alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 nuclear carbon atoms which may have a substituent, an alkylamino group having 3 to 30 carbon atoms which may have a substituent, and a substituent; An arylamino group having 6 to 30 carbon atoms which may be substituted, and an alkylsilyl group having 3 to 30 carbon atoms which may have a substituent An arylsilyl group having 6 to 30 carbon atoms which may have a substituent, and a carboxyl-containing group having 1 to 30 carbon atoms which may have a substituent.]]   The organic electroluminescent element in which the organic thin film layer which consists of the organic thin film layer which has at least one light emitting layer between an anode and a cathode is pinched | interposed, and at least 1 layer of the said organic thin film layer is in any one of Claims 1-3. An organic electroluminescence device comprising a transition metal complex compound having a metal carbene bond.   The organic electroluminescent element of Claim 4 in which the said light emitting layer contains the transition metal complex compound which has a metal carbene bond in any one of Claims 1-3 as a luminescent material.   The organic electroluminescent element of Claim 4 in which the said light emitting layer contains the transition metal complex compound which has a metal carbene bond in any one of Claims 1-3 as a dopant.   An electron injection layer and / or an electron transport layer is provided between the light emitting layer and the cathode, and the electron injection layer and / or the electron transport layer contains a π electron deficient nitrogen-containing heterocyclic derivative as a main component. 5. The organic electroluminescence device according to 4.   The organic electroluminescent element according to claim 4, wherein a reducing dopant is added to an interface region between the cathode and the organic thin film layer.

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