WO2007058255A1

WO2007058255A1 - Transition metal complex compound

Info

Publication number: WO2007058255A1
Application number: PCT/JP2006/322852
Authority: WO
Inventors: Kazushi Mashima; Masami Watanabe
Original assignee: Idemitsu Kosan Co., Ltd.; Osaka University
Priority date: 2005-11-17
Filing date: 2006-11-16
Publication date: 2007-05-24

Abstract

A transition metal complex compound with specified structure having a carbene bond; and a process for producing the same. Further, there is provided an organic EL device comprising a positive electrode and a negative electrode and, interposed therebetween, one or two or more organic thin-film layers including at least a luminescent layer, wherein at least one layer of the organic thin-film layers contains the transition metal complex compound having a metal carbene bond. The provided novel transition metal complex compound with a carbene bond exhibits electroluminescence properties and can provide an organic electroluminescence device of high luminous efficiency, and the process for producing the transition metal complex compound is provided.

Description

Transition metal complex compounds

Technical field

TECHNICAL FIELD [0001] The present invention relates to a transition metal complex compound, and more particularly to a transition metal complex compound having an electoluminescence property that can provide an organic electroluminescence element having high luminous efficiency and a method for producing the transition metal compound. It is.

Background art

[0002] Organic electoluminescence (EL) devices use 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. Self-luminous element. Report of low-voltage driven organic EL devices using stacked devices by Eastman Kodak's CW Tang et al. (CW Tang, SA Vanslyke, Applied Physics Letters, 51 卷, 913, 1987, etc.) ) Since then, research on organic EL devices using organic materials as constituent materials has been actively conducted. Tang et al. Used tris (8-hydroxyquinolinol aluminum) for the light-emitting layer and triphenyldiamine derivative for the hole-transporting 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, and increases the generation efficiency of excitons generated by recombination. For example, confining excitons. As in this example, the device structure of the organic EL device 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). The three-layer type is well known. In order to increase the recombination efficiency of injected holes and electrons in such a stacked structure element, the structure of the element and the formation method have been devised. The light-emitting material of the organic EL element is a tris (8-quinolinolato) aluminum complex. Luminescent materials such as chelate complexes, coumarin derivatives, tetraphenylbutadiene derivatives, distyrylarylene derivatives, oxadiazole derivatives, etc. are known, and it has been reported that they can emit light in the visible region from blue to red. Therefore, it is expected to realize a color display element (for example, see Patent Document 1). [0003] 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). In this way, high emission efficiency has been 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 recombine in an organic EL device, it is thought that singlet excitons and triplet excitons are generated at a ratio of 1: 3 due to the difference in spin multiplicity. Using this light emitting material, it is possible to achieve a light emission efficiency of 3 to 4 times that of a device using only fluorescence.

In such an organic EL device, the triplet excited state or triplet exciton is not sequentially quenched so that the anode, the hole transport layer, the organic light emitting layer, the electron transport layer (hole blocking layer), A structure in which layers are stacked such as an electron transport layer and a cathode has been used, and a host compound and a phosphorescent compound have been used for an organic light emitting layer (see, for example, Patent Document 2 and Patent Document 3). These patent documents are technologies related to phosphorescent materials that emit red to green light. In addition, techniques relating to a light emitting material having a blue emission color have been disclosed (see, for example, Patent Document 4, Patent Document 5, and Patent Document 6). However, these have a very short device lifetime, and in particular, Patent Documents 5 and 6 describe a ligand skeleton in which an Ir metal and a phosphorus atom are bonded, and these emit light blue but have weak bonds. The heat resistance is extremely poor. Patent Document 7 similarly 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 8 discloses a complex in which nitrogen atomic energy contained in different ring structures is bonded to a central metal, and a device using the same emits blue light, but the external quantum efficiency is as low as about 5%. It has become.

[0004] On the other hand, in recent years, studies have been made on transition metal complex compounds having metal carbene bonds (hereinafter sometimes referred to as carbene complexes) (for example, see Patent Document 9 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 orbit, and the combined force of the orbit into which the two electrons enter and the spin direction can have four types of structures. Is a singlet carbene, consisting of a sp ² hybrid occupied orbit and an empty 2p orbit. Traditionally, carbene complexes are short-lived 'unstable, and are intermediates or organic intermediates in organic synthesis reactions. Power that has been used as a synthetic conversion reagent such as addition to refin Around 1991, stable carbene complexes consisting of aromatic heterocyclic structures and stable carbene complexes consisting of non-aromatic cyclic structures were discovered. After that, the acyclic carbene complex was stably obtained by stabilizing with nitrogen and phosphorus. In addition, since the catalytic performance is improved by combining it with a transition metal as a ligand, in recent years, expectations for a stable carbene complex have increased in the catalytic reaction in organic synthesis.

In particular, in the olefin metathesis reaction, significant performance improvement has been found by adding or coordinating a stable carbene complex. In recent years, research has been conducted on the efficiency of the Suzuki coupling reaction, acid-selective hydroformylation of alkanes, and optically active carbene complexes. Application to the field is attracting attention.

In addition, specific examples of complexes having a carbene iridium bond include the following non-patent document 12 (tris (carbene) iridium complex that also has a non-heterocyclic carbene ligand force) and non-patent document 13 (monodentate coordination type mono-). Carbene iridium complex), but the application to the organic EL device field is described.

Patent Document 9 discloses the synthesis of an iridium complex having a carbene bond and its emission wavelength and device performance. 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 light-emitting devices in the visual wavelength range such as organic EL. Also, there was a problem in that impurities could be mixed during device fabrication because vacuum deposition could not be performed because the decomposition temperature was low or the molecular weight was high, and the complex was decomposed during the deposition.

Patent Document 1: JP-A-8-239655

Patent Document 2: U.S. Patent No. 6,097,147

Patent Document 3: International Publication WO01Z41512

Patent Document 4: US2001Z0025108 Publication

Patent Document 5: US 2002/0182441 Publication

Patent Document 6: Japanese Patent Laid-Open No. 2002-170684

Patent Document 7: Japanese Unexamined Patent Publication No. 2003-123982 Patent Document 8: Japanese Patent Laid-Open No. 2003-133074

Patent Document 9: International Publication WO05Z019373

Non-Patent Document 1: D. F. OBrien and M. A. Baldo et al "lmproved energy tr ansferin electrophosphorescent devices Applied Physics Letters Vol. 74 No. 3, pp 442-444, Januaryl8, 1999

Non-Patent Document 2: M. A. Baldo et al Very high-efficiency green organic li ght -emitting devices based on electrophosphorescence "Applied Phys ics Letters Vol. 75 No. 1, pp4-6, July 5, 1999

Non-Patent Document 3: Chem. Rev. 2000, 100, p39

Non-Patent Document 4 Am. Chem. Soc., 1991, 113, p361

Non-Patent Document 5: Angew. Chem. Int. Ed., 2002, 41, pi 290

Non-Patent Document 6 Am. Chem. Soc., 1999, 121, p2674

Non-Patent Document 7: Organometallics, 1999, 18, p2370

Non-Patent Document 8: Angew. Chem. Int. Ed., 2002, 41, pl363

Non-Patent Document 9: Angew. Chem. Int. Ed., 2002, 41, pi 745

Non-Patent Document 10: Organometallics, 2000, 19, p3459

Non-Patent Document 11: Tetrahedron Asymmetry, 2003, 14, p951

Non-Patent Document 12: Organomet. Chem., 1982, 239, C26-C30

Non-Patent Document 13: Chem. Commun., 2002, ρ2518

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a novel transition metal complex compound and a method for producing a transition metal compound that realize an organic EL device having high luminous efficiency. To do.

Means for solving the problem

[0007] As a result of intensive studies to achieve the above object, the present inventors have used a transition metal complex compound having a specific structure having a metal carbene bond represented by the following general formula (1). Finding that an organic EL device with high luminous efficiency can be obtained and completing the present invention It came.

That is, the present invention provides a transition metal complex compound having a metal carbene bond represented by the following general formulas (1), (3) and (4).

[Chemical 1] 厂

[In the general formula (1), C (carbon atom) → M represents a metal carbene bond, the bond indicated by a solid line (1) indicates a covalent bond, and the bond indicated by an arrow (→) indicates a coordinate bond. . M represents a metal atom of iridium (Ir), platinum (Pt), rhodium (Rh) or palladium (Pd). L ¹ and L ² each independently represent a monodentate ligand or a bridged bidentate ligand (L ¹ -L ² ) in which L ¹ and L ² are bridged. k is an integer from 1 to 3, i is an integer from 0 to 2, and k + i represents the valence of metal M. j represents an integer of 0 to 4. When there are a plurality of i and j, L ¹ and L ² may be the same or different, and adjacent ones may be bridged together.

L ¹ is a monovalent aromatic hydrocarbon group having 6 to 30 nuclear carbon atoms which may have a substituent, or a monovalent heterocyclic group having 3 to 30 nucleus atoms which may have a substituent. A monovalent carboxyl-containing group having 1 to 30 carbon atoms, a monovalent amino group or a hydroxyl group-containing hydrocarbon group, and a substituent. A cycloalkyl group having 3 to 50 nuclear carbon atoms, which may have a substituent, an alkyl group having 1 to 30 carbon atoms, or a substituent which may have a cycloalkyl group having 2 to 30 carbon atoms , An aralkyl group having 7 to 40 carbon atoms which may have a substituent, and when L ¹ and L ² are bridged, a divalent group of each of the above groups,

L ² is a heterocyclic ring having 3 to 30 nuclear atoms that may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms that may have a substituent, a carboxylic acid amide having 1 to 30 carbon atoms, May have a substituent, phosphine which may have a substituent, iso-tolyl which may have a substituent, It may have a substituent, may have an ether having 1 to 30 carbon atoms, or may have a substituent! チ may have a thioether having 1 to 30 carbon atoms, or may have a substituent. The double bond-containing compound is a monovalent group of the above-mentioned ligands when L ¹ and L ² are cross-linked.

Z ¹ is an atom that forms a covalent bond with the metal M and is a carbon, silicon, nitrogen, or phosphorus atom, and Z ² is an atom that forms a covalent bond with the substituent R ¹ , such as carbon, A ring which is a nitrogen or phosphorus atom and includes Z ¹ and Z ² , and the B ring may have an aromatic hydrocarbon group having 3 to 40 nuclear carbon atoms or a substituent which may have a substituent. It is a good heterocyclic group having 3 to 40 nuclear atoms, Z ³ represents a nitrogen atom or CR ^2, and when CR ² is plural, plural R ² may be the same or different.

R ¹ and R ² are each independently a hydrogen atom, halogen atom, thiociano group, or cyano group, -tro group, —S (= 0) R ¹⁸ group, or —S (= 0) R ¹⁸ , substituted Carbon number which may have a group

2

An alkyl group having 1 to 30 carbon atoms, a substituent, a halogenated alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent, a substituent V, a cycloalkyl group having 3 to 30 nuclear carbon atoms, a substituent, a aralkyl group having 7 to 40 carbon atoms, and a carbon group that may have a substituent 2 -30 alkenyl group, optionally having 3-30 nuclear atoms, a heterocyclic group having 1-30 carbon atoms, optionally having 1-30 carbon atoms, having a substituent. Good 6-30 carbon atomyloxy group, which may have a substituent Alkylamino group having 3-30 nuclear atoms, which may have a substituent, 6-30 carbon atom amino group, substituted An alkylsilyl group having 3 to 30 nuclear atoms which may have a group, an arylsilylsilyl group having 6 to 30 carbon atoms which may have a substituent, and a carboxyl-containing group having 1 to 30 carbon atoms. When Z ³ is CR ^2, R ¹ and R ² may be crosslinked.

(R ¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, a substituted group. May have an aromatic hydrocarbon group having 6 to 30 carbon atoms, may have a substituent! May have a cycloalkyl group having 3 to 50 carbon atoms, or a substituent. It may have a aralkyl group having 7 to 40 carbon atoms, a substituent, a alkenyl group having 2 to 30 carbon atoms, or a substituent, a heterocyclic group having 3 to 30 nuclear atoms, An optionally substituted alkoxy group having 1 to 30 carbon atoms, which may have a substituent, an aryloxy group having 6 to 30 nuclear carbon atoms, or a substituent, which has 3 to 30 carbon atoms of An alkylamino group, an arylamino group having 6 to 30 carbon atoms which may have a substituent, a substituent, an alkylsilyl group having 3 to 30 carbon atoms, and a substituent; It is a carboxyl-containing group having 1 to 30 carbon atoms which may have an arylylsilyl group having 6 to 30 carbon atoms or a substituent. )

When k is more than one,

Rings A and B may be the same or different and may be bridged by adjacent ones. ]

[0010] [Chemical 2]

[In general formula (3), C (carbon atom) → M represents a metal carbene bond, and the bond indicated by an arrow (→) represents a coordinate bond. M is the same as above, and L ² represents a monodentate ligand. j is the same as above, and when j is plural, each L ² may be the same or different, or may be cross-linked.

L ² is the same ligand as described above, and L ³ is a super strong acid, a carboxylic acid, an aldehyde, a ketone, an alcohol, a thioalcohol, a phenol, an amine having a pKa value of 10 or less. Amides, amides, aromatics or alkane conjugate bases, or hydrogen ions or halide ions.

Z ¹ is a carbon, silicon, nitrogen or phosphorus atom;

Z ³ and R ¹ are the same as described above.

[0012] [Chemical 3]

[0013] [In the general formula (4), C (carbon atom) → M represents a metal carbene bond, the bond indicated by a solid line (1) is a covalent bond, and the bond indicated by an arrow (→) is a coordinate bond. Means. M is the same as described above, and L ² represents a monodentate ligand. j is the same as above, and when j is plural, each L ² may be the same or different and may be cross-linked.

L ² is the same ligand as defined above, L ³ ,

Ζ ³ and R ¹ are the same as above.

[0014] The present invention also includes reacting an iridium compound represented by the following general formula (5) and an imidazolium salt represented by the following general formula (6) in the presence of a solvent and a base. The present invention provides a method for producing a transition metal compound having a metal carbene bond for producing a transition metal compound represented by

[Chemical 4]

[0015] [In the general formulas (5-7), C (carbon atom) → Ir (iridium) represents a metal carbene bond, the bond indicated by a solid line (one) represents a covalent bond, and an arrow (→ The bond indicated by) means a coordination bond. L ² represents a monodentate ligand. j is the same as described above, and when j is plural, each L ² may be the same or different and may be cross-linked.

L ² is the same ligand as defined above, L ³ ,

Ζ ³ and R ¹ are the same as above.

[0016] 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 metal An organic EL element containing a transition metal complex compound having a carbene bond is provided.

The invention's effect

[0017] The transition metal complex compound having a metal carbene bond of the present invention can provide an organic EL device having electoluminescence properties and high luminous efficiency. Moreover, according to the method for producing a transition metal complex compound of the present invention, the transition metal complex compound can be produced efficiently. Brief Description of Drawings

FIG. 1 is a diagram showing a ¹ H-NMR ^ vector of intermediate c obtained in Example 1.

FIG. 2 is a diagram showing a ¹ H-NMR ^ vector of intermediate d obtained in Example 1.

FIG. 3 is a diagram showing a ¹ H-NMR spectrum of transition metal complex compound 1 obtained in Example 1.

FIG. 4 is a diagram showing a ¹ H-NMR spectrum of transition metal complex compound 1 obtained in Example 2.

FIG. 5 is a diagram showing cyclic voltammetry of the transition metal complex compound 1 obtained in Example 3.

FIG. 6 is an X-ray crystal structure analysis of transition metal complex compound 1 obtained in Example 3.

FIG. 7 shows a ¹ H-NMR spectrum of transition metal complex compound 2 obtained in Example 4.

FIG. 8 is a view showing cyclic voltammetry of the transition metal complex compound 1 obtained in Example 4.

FIG. 9 is a diagram showing an X-ray crystal structure analysis of transition metal complex compound 2 obtained in Example 4.

FIG. 10 is a diagram showing a ¹ H-NMR spectrum of transition metal complex compound 3 obtained in Example 5.

FIG. 11 is a diagram showing a ¹ H-NMR spectrum of transition metal complex compound 4 obtained in Example 6.

FIG. 12 is a view showing cyclic voltammetry of the transition metal complex compound 4 obtained in Example 6.

FIG. 13 is a diagram showing an emission spectrum at room temperature of the transition metal complex compound 4 obtained in Example 6.

FIG. 14 is a graph showing an emission spectrum at 77K of the transition metal complex compound 4 obtained in Example 6.

BEST MODE FOR CARRYING OUT THE INVENTION 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 formulas (1), (3) and (4).

Hereinafter, the general formula (1) will be described.

[Chemical 5]

[0020] In the general formula (1), C (carbon atom) → M represents a metal carbene bond, a bond indicated by a solid line (-) represents a covalent bond, and a bond indicated by an arrow (→) represents a coordinate bond. means.

In the general formula (1), M represents a metal atom of iridium (Ir), platinum (Pt), rhodium (Rh) or palladium (Pd), and Ir is preferred! /.

In the general formula (1), L ¹ and L ² each independently represent a monodentate ligand or a bridged bidentate ligand (L ¹ L ² ) in which L ¹ and L ² are bridged. k is an integer from 1 to 3, i is an integer from 0 to 2, and k + i represents the valence of metal M. j represents an integer of 0 to 4. When i and j are plural, L ¹ and L ² may be the same or different from each other, and may be cross-linked with each other. In the general formula (1), L ¹ is a monovalent aromatic hydrocarbon group having 6-30 nuclear carbon atoms which may have a substituent, and 3-30 nuclear atoms optionally having a substituent. A monovalent heterocyclic group, a monovalent carboxyl-containing group having 1 to 30 carbon atoms which may have a substituent, a monovalent amino group or a hydroxyl group-containing hydrocarbon group which may have a substituent, a substituent; A cycloalkyl group having 3 to 50 nuclear carbon atoms, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a substituent group having 2 to 30 carbon atoms. These alkenyl groups, substituents, aralkyl groups having 7 to 40 carbon atoms, and when L ¹ and L ² are crosslinked, are divalent groups of the above groups.

[0021] The aromatic hydrocarbon group is preferably one having a nuclear carbon number of 6 to 18, for example, a phenol group, 1 naphthyl group, 2 naphthyl group, 1 anthryl group, 2 anthryl group, 9-a Enthryl group, 1 phenanthryl group, 2 phenanthryl group, 3 phenanthryl group, 4 phenanthryl group, 9 phenanthryl group, 1 naphthacene group, 2 naphthacetyl group, 9-naphthaphthal group, 1-pyrole group , 2 pyreyl group, 4 pyreyl group, 2 biphenyl group, 3—biphenyl group, 4-biphenyl group, p terferyl group 4 —yl group, p terferlu group 3— P-group, p-Terfer-Lu 2-yl group, m-Ter-Fel-Lu 4-Yel group, m-Ter-Fel-Lu 3-Il group, m-Ter-Fel-Lu 2-Yil group, o-Tolyl group, m-Tolyl group Group, ρ-tolyl group, p-t-butylphenol group, p- (2-phenylpropyl) phenol group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1 anthryl group, 4, -Methylbiphenyl group, 4 "-tert-butyl-p-terferyl group, o Tam groups, m-tama groups, p-tam groups, 2, 3 xylylene groups, 3, 4 xylyl groups, 2, 5 xylylene groups, mesitylene groups, perfluorofuryl Groups, etc. and those having these as divalent groups.

Of these, a 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 and the like and divalent groups thereof.

Preferred examples of the heterocyclic group include those having 3 to 18 nuclear atoms. For example, 1 pyrrolyl group, 2 pyrrolyl group, 3 pyrrolyl group, birazinyl group, 2 pyridyl group, 1 imidazolyl group, 2-imidazolyl group 1-pyrazolyl group, 1-indolidyl group, 2-indolidyl group, 3 indolidyl group, 5-indolidyl group, 6-indolidyl group, 7-indolidyl group, 8 indrigid group Group, 2 imidazopyridyl group, 3 imidazopyridyl group, 5 imidazopyridyl group, 6-imidazopyridyl group, 7-imidazopyridyl group, 8-imidazolidyl group, 3 pyridyl group, 4-pyridyl 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-Isoy Group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2 furyl group, 3 furyl group, 2 benzofural group, 3 benzofural group, 4 benzofuran Group, 5 monobenzofural group, 6 benzofural group, 7 benzofural group, 1 isobenzozofural group, 3-isobenzofural group, 4 isobenzozofural group Group, 5-isobenzofura Group, 6-isobenzofuller group, 7-isobenzofuller group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group Group, 1 isoquinolyl group, 3 isoquinolyl group, 4 isoquinolyl group, 5 isoquinolyl group, 6-isoquinolyl group, 7 isoquinolyl group, 8 isoquinolyl group, 2 quinoxalinyl group, 5 quinoxalyl group, 6 quinoxalinyl group, 1 primary rubazolyl Group, 2-force rubazolyl group, 3-force rubazolyl group, 4 one-force rubazolyl group, 9 one-force rubazolyl group, 13 carboline 1 yl, j8-carboline-3-yl, j8-carboline-4 yl j8—carboline—5-yl, 13 carboline 6-yl, j8—carboline 7—yl, j8—carboline 8—yl, 13—carboline-9 yl, 1 phenanthridyl group, 2 phenanthuri Diene group, 3 pheny rigid group, 4 phenanthridyl group, 6-phenanthridyl group, 7-phenanthridyl group, 8 phenanthridyl group, 9 phenanthridyl group, 10 phenanthridyl group Group, 1-ataridyl group, 2-ataridyl group, 3-ataridyl group, 4-ataridyl group, 9-ataridyl group, 1,7 phenanthroline-2-yl group, 1, 7 Phenanthrin Phosphorus— 3-yl group, 1, 7 Phenanthroline— 4-yl group, 1, 7 Phenanthrolin— 5- — group, 1, 7 Phenanthroline— 6-yl group, 1, 7 Phenanthroline— 8 —Yl group, 1,7 phenanthroline—9—yl group, 1,7 phenanthroline—10—yl group, 1,8 —phenanthroline 1—2 group, 1,8 phenanthroline 1—yl group, 1,8 phenanthroline 4-yl group, 1,8 phenanthroline 5-l group 1,8 phenanthroline —6-yl group, 1,8 phenanthroline—7-yl group, 1,8 phenanthroline—9—yl group, 1,8 phenanthroline 10-yl group, 1,9 phenanthroly 2-yl group, 1, 9 phenanthroline— 3-yl group, 1, 9 phenanthroline— 4-yl group, 1, 9 phenanthroline— 5-yl group, 1, 9 phenanthroline— 6-yl 1, 9 phenanthroline—7—yl group, 1,9 phenanthroline—8—yl group, 1,9 phenanthroline—10 —yl group, 1,10 phenanthroline—2-yl group, 1, 10 Phenylanthroline—3-yl group, 1, 10-Phenanthhroline—4-yl group, 1,10-Phenanthroline—5-yl group, 2,9 Phenanthroline 1-yl group, 2,9 Phenanthroline 3-— Group, 2, 9 phenanthroline — 4-yl group, 2, 9 phenanthroline— 5-yl group, 2, 9 phenanthrene 6-yl group, 2, 9 phenanthroline 7-yl group, 2, 9 phenanthroline 8 —Yl group, 2, 9 phenanthroline— 10—yl group, 2,8 phenanthroline— 1—yl group, 2,8 phenanthroline—3—yl group, 2,8 phenanthroline—4-yl group 2, 8—Phenanthhroline 1-5—yl group, 2, 8 Phenanthroline 6—yl group, 2, 8 Phenanthroline 7—yl group, 2, 8 Phenanthroline 9—yl group, 2, 8 Phenanthroline — 10—yl group, 2, 7 Phenanthroline 1—yl group, 2, 7 Phenanthroline 1—yl group, 2, 7 Phenanthroline 4—yl group, 2, 7 Phenanthroline 1—yl group 2, 7 phenanthroline 6-yl group, 2, 7 phenanthroline 1-yl group, 2, 7 phenanthroline 9-yl group, 2, 7 phenanthroline 10-yl group, 1 phenadyl group, 2 Phenadyl group, 1 phenothiazyl group, 2 phenothiazyl group, 3 phenothia Diol group, 4-phenothiazyl group, 10-phenothiazyl group, 1-phenoxazinyl group, 2-phenoxazyl group, 3-phenoxazyl group, 4-phenoxazyl group, 10-phenoxazyl group, 2-oxazolyl group , 4-Oxazolyl group, 5-Oxazolyl group, 2 Oxadiazolyl group, 5 Oxadiazolyl group, 3 Furazanyl group, 2 Cheel group, 3 Cheer group, 2 Methyl pyrrole 1 yl group, 2 Methyl pyrrole luo 3-yl Group, 2 methyl pyrrole 4-yl group, 2 methyl pyrrole 5-yl group, 3 methyl pyrrole 1-yl group, 3 methyl pyrrole 2-yl group, 3 methyl pyrrole 4-yl group, 3 Methyl pyrrole 5—yl group, 2 t-butyl pyrrole 4-yl group, 3— (2 propylpropyl) pyrrole 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, 2 t-butyl 3 indolyl group, 4 t-butyl 3-indolyl group, pyrrolidine, virazolidine, piperazine And those having these as a divalent group.

Among these, 2-pyridyl group, 1-indolidyl group, 2-indolidyl group, 3-indolidyl group, 5-indolidyl group, 6-indolidyl group, 7 —Indolizyl group, 8 Indolizyl group, 2 Imidazopyridyl group, 3 Imidazopyridinyl group, 5 Imidazopyridinyl group, 6—Imidazopyridyl group, 7—Imidazopyridyl group, 8—Imidazopyridyl group Group, 3-pyridyl group, 4 pyridyl group, 1 indolyl group, 2 indolyl group, 3—indolyl group, 4 indolyl group, 5—indolyl group, 6—indolyl group, 7—in Drill 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 force rubazolyl group, 3 force Rubazolyl group, 4 rubazolyl group, 9 carbazolyl group and these are divalent groups.

[0023] Examples of the carboxyl-containing group include an ester bond (-C (= 0) 0-), a methyl ester, an ethyl ester, a butyl ester, and the like, and those using these as a divalent group.

Examples of the cycloalkyl and cycloalkylene groups 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 2- And norborol groups and the like and divalent groups thereof.

[0024] As the alkyl group and alkylene group, those having 110 carbon atoms are preferable, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group. Group, n pentyl group, n xyl group, n ptyl 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 xadecyl group, n ptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1 pentylhexyl group, 1-butylpentyl group, 1 ptyloctyl group, 3-methylpentyl group, hydroxymethyl group 1-hydroxyethyl group, 2 hydroxychetyl group, 2 hydroxyisobutyl group, 1,2 dihydroxyethyl group, 1,3-di Droxyisopropyl group, 2,3 dihydroxy-tert-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-tbutyl group, 1,2,3 triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2cyanoisobutyl group, 1,2 Dicanoethyl group, 1,3 dicyanoisopropyl group, 2,3 dicyanol t-butyl group, 1,2,3 tricyanopropyl group, ditromethyl group, 1-troethyl group, 2--troethyl group, 1,2-dinitroethyl group 2, 3, di-tallow t-butyl, 1, 2, 3 tri-tropropyl, cyclopentyl, cycl Examples thereof include a mouth hexyl group, a cyclooctyl group, a 3,5-tetramethylcyclohexyl group, and the like, which are divalent groups.

Among these, methyl, ethyl, propyl, isopropyl, n-butyl, sbutyl, isobutyl, tbutyl, n-pentyl, n-hexyl, and n- are preferred. Ptyl group, n-octyl group, n-nor 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, 1 pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclo Hexyl groups and these are divalent groups.

[0025] The alkaryl group and the alkellene group are preferably those having 2 to 16 carbon atoms. For example, bur group, aralkyl group, 1-butenyl group, 2 butenyl group, 3 butenyl group, 1, 3 Butane gel group, 1-methyl beryl group, styryl group, 2,2 diphenyl beryl group, 1,2-diphenyl beryl group, 1-methyl beryl group, 1,1-dimethyl allyl group, 2-methyl beryl group 1-Furaryl group, 2-Feraryl group, 3-Feraryl group, 3, 3-Difuryl-Rulyl group, 1,2 Dimethylaryl group, 1-Fu-Lu 1-Butul group, 3-Fuenyl 1-Butenyl And a group having these as a divalent group, preferably a styryl group, a 2,2-diphenyl-vinyl group, a 1,2-diphenyl-vinyl group, and a divalent group thereof. It is what.

[0026] Preferred examples of the aralkyl group and the aralkylene group include those having 7 to 18 carbon atoms, such as 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-a naphthylethyl group, 1-a naphthylisopropyl group, 2-a naphthylisopropyl group, 13 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, ρ-methinolevendinore group, m-methenoleveninore group Group, o-methinolevenzinole group, p-capped benzyl group, m-capped benzyl group, o-capped benzyl group, p-bromobenzyl group, m Bromobenzyl group, o Bromobenzyl group, p-odobenzyl group, m-odobenzyl group, o-odobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group Nyl group, o aminobenzinole group, p ditrobenzinole group, m-ditrobenzinole group, o ditrobenzinole group, p cyanobenzyl group, m-cyanobenzyl group, o cyanobenzyl group, 1-hydroxy 1 2— Those having a divalent group such as a phenol isopropyl group, 1-chloro 2-phenyl isopropyl group, and the like, preferably a benzyl group, a p-cyanobenzyl group, an m-cyanobenzyl group, an o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, and these As the amino group or hydroxyl group-containing hydrocarbon group, an amino group having each hydrocarbon group represented by L ¹ and a hydrogen atom of the hydrocarbon group replaced with a hydroxyl group Are listed.

In the general formula (1), L ² is a heterocyclic ring having 3 to 30 nuclear atoms which may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms which may have a substituent, A carboxylic acid amide having 1 to 30 carbon atoms, an amine that may have a substituent, a phosphine that may have a substituent, an iso-tolyl that may have a substituent, and a substituent. From ethers having 1 to 30 carbon atoms, substituents, thioethers having 1 to 30 carbon atoms, or substituents having double bond containing compounds having 1 to 30 carbon atoms When L ¹ and L ² are bridged, they are monovalent groups of the respective ligands.

[0028] Examples of the heterocyclic ring include those in which the group in the example similar to that described above for L ¹ is zero-valent.

Examples of the carboxylic acid esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl benzoate, ethyl benzoate, methyl 2-pyridinecarboxylate, ethyl pyridinecarboxylate, 3 Methyl pyridine carboxylate, ethyl 3-pyridinecarboxylate, 4 methyl pyridinecarboxylate, 4 ethyl pyridinecarboxylate, methyl chloroacetate, ethyl chloroacetate, methyl 2-pyridine acetate, ethyl pyridine pyridine, 3 Methyl pyridine acetate, 3 Pyridine acetate Examples include chill, methyl 4-pyridineacetate, ethyl 4-pyridineacetate, methyl 2-pyrrolecarboxylate, methyl 3-pyrrolecarboxylate, methyl 2-thiophenecarboxylate, and methyl 3-thiophenecarboxylate.

[0029] Examples of the carboxylic acid amide include N, N dimethylformamide, N, N dimethylacetamide, N, N dimethylbenzoic acid amide, N, N dimethyl-2-pyridine, rubonic acid amide, N, N dimethyl-3- Pyridinecarboxylic acid amide, N, N dimethyl-4-pyridinecarboxylic acid amide, N, N dimethylphenol acetate, N, N dimethyl-2-pyridine acetate, N, N dimethyl-3 pyridine acetate, N, N dimethyl Cyl-4 pyridineacetamide, N, N dimethyl-2-pyrrolecarboxylic acid amide, N, N dimethyl-3 pyrrolecarboxylic acid amide, N, N dimethyl-2-thiophenecarbonic acid amide, N, N dimethyl-3-thiophenecarboxylic acid amide , N-methylformamide, N-methylacetamide, N-methylbenzoic acid amide, N-methyl-2-pyridine Rubonic acid amide, N-methyl-3-pyridinecarboxylic acid amide, N-methyl-4-pyridincarboxylic acid amide, N-methyl-phenylacetic acid amide, N-methyl-2-pyridineacetic acid amide, N-methyl-3-pyridineacetic acid amide, N —Methyl-4 pyridineacetamide, N-methyl-2-pyrrolecarboxylic amide, N-methyl-3-pyrrolecarboxylic amide, N-methyl-2 thiophenecarboxylic amide, N-methyl-3 thiophenecarboxylic amide, acetoamide, benzoic amide , 2 pyridinecarboxylic acid amide, 3 pyridine force rubonic acid amide, 4 pyridinecarboxylic acid amide, phenylacetic acid amide, 2 pyridineacetic acid amide, 3 pyridineacetic acid amide, 4 pyridineacetic acid amide, 2 pyrrolecarboxylic acid amide, 3 pyrrolecarboxylic acid Acid amide, 2 thiophenecarboxylic Amide, 3 Chiofenkaru Bonn acid amide.

[0030] Examples of the amine include triethylenamine, tri-n-propylamine, tri-n-butylamine, N, N dimethylaniline, methyldiphenylamine, triphenylamine, dimethyl (2 Pyridine) amine, dimethyl (3 pyridine) amine, dimethyl (4 pyridine) amine, methylbis (2 pyridine) amine, methylbis (3-pyridine) amine, methylbis (4-pyridine) amine, tris (2 pyridine) amine, tris (3 pyridine) amine, tris (4 pyridine) amine, diisopropylamine, di-n-propylamine, di-n-butylamine, N -Methylamine, methylphenolamine, diphenylamine, methyl (2-pyridine) amine, methyl (3 pyridine) amine, methyl (4 pyridine) amine, methyl (2 pyridine) amine, methyl (3 pyridine) amine, Methyl (4 pyridine) amine, bis (2 pyridine) amine, n-propylamine, n-butylamine, a-line, (2 pyridine) amine, (3 pyridine) amine, (4 pyridine) amine, (2 pyridine) amine, (3 Pyridine) amine, (4 Pyridine) amine, Pyridine, 2-Methylolepyridine, 3-Methylenopyridine, 4-Methylenopyridine, 2 Trifluoromethylpyridine, 3-Trifluoromethylpyridine, 4 Trifluoromethyl Examples include pyridine and N-methylbilol.

[0031] Examples of the phosphine include those obtained by replacing nitrogen of the amine with phosphorus.

Examples of the iso-tolyl include butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, phenol isocyanide, 2-tolyl isocyanide, 3 tolyl isocyanide, 4 tolyl isocyanide, 2 pyridine isocyanide, 3 pyridine isocyanide. 4-pyridine isocyanide, benzyl isocyanide and the like. Examples of the ether include jetyl ether, di- _n -propyl ether, di-n-butinoleethenole, diisobutinoleethenole, di-sec butinoleethenole, di-t-butyl ether, anisole, diphenyl ether, furan, Tetrahydrofuran, dioxane and the like can be mentioned.

Examples of the thioether include those obtained by replacing oxygen in the ether with sulfur.

Examples of the compound having a double bond having 1 to 30 carbon atoms include ethylene, propylene, 1-butene, 1 pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1 eicosene. 2—Butene, 2—Pentene, 2—Hexene, 2—Heptene, 2 —Year Kten, 2 Nonene, 2 Decene, 2 Eicosen, 3 Hexene, 3 Heptene, 3 —Otaten, 3—Nonene, 3—Decene , 3-eicosene, isobutene, styrene, a-methylstyrene, 13-methylstyrene, butadiene, isoprene, stilbene, etc.

[0032] In the general formula (1), Z ¹ is an atom that forms a covalent bond with the metal M, and includes carbon, silicon, A nitrogen or phosphorus atom, and Z ² is an atom that forms a covalent bond with the substituent R ¹ and is a carbon, silicon, nitrogen or phosphorus atom, and the A ring and the B ring containing Z ¹ and Z ² are V, an aromatic hydrocarbon group having 3 to 40 carbon atoms, or a heterocyclic group having 3 to 40 nuclear atoms.

Examples of this aromatic hydrocarbon group are the same as those mentioned above, and examples of this aromatic heterocyclic group include those which are aromatic heterocyclic groups among the examples of the heterocyclic group. It is

[0033] Among them, A ring containing R ¹ and Z ¹ and Z ²

[Chemical 6]

Is preferably a structure represented by the following. In the following example, the same example can be given when M is other than the force Ir exemplified as Ir. X represents a ring structure including an adjacent B ring. In addition, the bond between X and Ir (→) is omitted.

[0034] [Chemical 7]

[Chemical 8]

Is preferably a structure represented by the following. In the following example, the same example can be given when M is other than the force Ir exemplified as Ir. The A ring structure containing R ¹ and Z ¹ and Z ² is simply abbreviated as A ring. Also, the A ring and Ir bond (one) is omitted.

[0036] [Chemical 9]

[0037] [Chemical 10]

In the general formula (1), Z ³ represents a nitrogen atom or CR ^2, and when CR ² is plural, plural R ² may be the same or different! /! /.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a thiociano group, a cyano group, a nitro group, a —S (= 0) R ¹⁸ group, or —S (= 0) R ¹⁸ , a substituent. Carbon number that may have

2

(In the above, each R ¹⁸ is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, Aromatic hydrocarbon group with 6 to 30 carbon atoms, may have a substituent! A cycloalkyl group having 3 to 50 carbon atoms, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, a substituent, a alkenyl group having 2 to 30 carbon atoms, and a substituent. Yes! Heterocyclic group having 3 to 30 nucleus atoms, alkoxy group having 1 to 30 carbon atoms which may have a substituent, and substituents having 6 to 30 nucleus carbon atoms May have an aryloxy group, a substituent, an alkylamino group having 3 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms which may have a substituent, or a substituent, may have a carbon number It may be an alkylsilyl group having 3 to 30 carbon atoms, a substituent, an arylsilylsilyl group having 6 to 30 carbon atoms, or a substituent, or a carboxyl-containing group having 1 to 30 carbon atoms. )

The alkyl group is preferably one having 1 to LO 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, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2 hydroxyisobutyl, 1,2 dihydroxyethyl, 1,3 Droxyisopropyl group, 2, 3 dihydroxy-tert-butyl group, 1, 2, 3 trihydroxypropyl group, aminoamino 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-cianoethyl group, 2 cyanoethyl group, 2 cyano Isobutyl 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-troethyl group, 1,2 dinitroethyl group, 2,3 di-tallow t-butyl group, 1,2,3 tri-tropropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclohexyl Group, and the like.

Of these, methyl, ethyl, propyl, isopropyl, n-butyl, sbutyl, isobutyl, tbutyl, n-pentyl, and n-hexyl are preferred. Group, n-heptyl group, n-octyl group, n-nor 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, 1 pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, 3, 5-tetramethylcyclohexyl group.

[0040] The halogenated alkyl group is preferably one having 1 to 10 carbon atoms. For example, a chloromethyl group, a 1-chlorooctyl group, a 2-chloroethyl group, a 2-chloroisobutyl group, 1 , 2-Dichlorodiethyl, 1,3 Dichlorodiethyl, 2,3 Dichloro-t-butyl, 1,2,3 Tricyclodipropyl, bromomethyl, 1 bromoethyl, 2 bromoethyl, 2 bromoisobutyl 1,2 dibromoethyl group, 1,3 dibromoisopropyl group, 2,3 dib-mouthed tert-butyl group, 1,2,3 tribromopropyl group, odomethyl group, 1- odoethyl group, 2-- odoethyl group, -2- odoisobutyl 1, 2—Jodoethyl group, 1,3 Jodoisopropyl group, 2, 3 Jodo t butyl group, 1, 2, 3 Triodopropyl group, Fluoromethyl group, 1 Fluoromethyl group, 2-F Fluoromethyl group, 2-fluoroisobutyl group, 1,2-difluoroethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorocyclohexyl Groups and the like.

Of these, preferred are a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, and a perfluorocyclohexyl group.

[0041] The aromatic hydrocarbon group is preferably one having a nuclear carbon number of 6 to 18, for example, a phenol group, 1 naphthyl group, 2 naphthyl group, 1 anthryl group, 2 anthryl group, 9-a Enthryl group, 1 phenanthryl group, 2 phenanthryl group, 3 phenanthryl group, 4 phenanthryl group, 9 phenanthryl group, 1 naphthacene group, 2 naphthacetyl group, 9-naphthaphthal group, 1-pyrole group , 2 pyreyl group, 4 pyreyl group, 2 biphenyl group, 3—biphenyl group, 4-biphenyl group, p terferyl group 4 —yl group, p terferlu group 3— P-group, p-terferreux 2—sil-group, m-terferreux 4 Group, m-terferyl 3-myl group, m-terferu 2-yl group, o-tolyl group, m-tolyl group, ρ-tolyl group, p-t-butylphenol 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 "-tert-butyl-p-terferyl 4-yl group , O-tamal group, m-tamer group, p-tame group, 2, 3 xylylene group, 3, 4 xylylene group, 2, 5 xylylene group, mesitylene group, perfluoro A phenyl group etc. are mentioned.

Of these, a 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. Groups and the like.

As the aralkyl group, those having 7 to 18 carbon atoms are preferred, for example, a benzyl group,

1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, tert-butyl, α-naphthylmethyl, 1α-naphthyl, 2- a naphthylethyl group, 1-a naphthylisopropyl group, 2-a naphthinoreisopropinole group, β-naphthinoremethinole group, 1-β-naphthinoreethinore group,

2-β-naphthylethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, 1-pyrrolylmethyl, 2- (1-pyrrolyl) ethyl, ρ-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p Chloro-benzyl group, m-Cloro-benzyl group, o Chloro-benzyl group, p-Bromobenzyl group, m-Bromobenzyl group, o-Bromobenzyl group, p-Chodobenzyl group, m-Chodobenzyl group, o-Chodobenzyl group , P Hydroxybenzyl group, m-hydroxybenzyl group, o Hydroxybenzyl group, ρ Amaminobenzyl group, m-Aminobenzyl group, o Amaminobenzyl group, p Nitrobenzyl group, m--Trobenzyl group, o -Trobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-1,2-phenol isop A propyl group, a 1 chloro-2-phenylisopropyl group, and the like, preferably a benzyl group ゝ p-Cyanobenzyl group, m-Cyanobenzyl group, o-Cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group.

[0043] The alkenyl group is preferably one having 2 to 16 carbon atoms. For example, a bur group, a allyl group, a 1-butur group, a 2 butur group, a 3 butur group, a 1, 3 butane angel group. , 1-methylvinyl group, styryl group, 2,2-diphenyl-vinyl group, 1,2-diphenyl-vinyl group, 1-methylaryl group, 1,1-dimethylaryl group, 2-methylaryl group, 1-phenyl group Examples include a ruaryl group, a 2-furaryl group, a 3-furaryl group, a 3,3 diphenyl-ruaryl group, a 1,2 dimethylaryl group, a 1-fluoro 1-butur group, and a 3-fluoro 1-butenyl group. Preferably, they are a styryl group, a 2,2-divinylvinyl group, and a 1,2-diphenylvinyl group.

[0044] The heterocyclic group preferably has 3 to 18 nuclear atoms. For example, 1 pyrrolyl group, 2 pyrrolyl group, 3 pyrrolyl group, birazinyl group, 2 pyridyl group, 1 imidazolyl group, 2 —Imidazolyl group, 1-pyrazolyl group, 1-indolidyl group, 2-indolidyl group, 3 indolidyl group, 5-indolidyl group, 6-indolidyl group, 7-indolidyl group, 8 Indolizyl group, 2 Imidazopyridyl group, 3 Imidazopyridyl group, 5 Imidazopyridyl group, 6-Imidazopyridyl group, 7-Imidazopyridyl group, 8—Imidazopyridyl group, 3 Pyridyl group Group, 4-pyridyl 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— Soindolyl group, 4-Isoindryl group, 5-Isoindolyl group, 6-Isoindolyl group, 7-Isoindolyl group, 2 Furyl group, 3 Furyl group, 2 Benzofural group, 3 Benzofural group, 4 Benzofura group Group, 5 monobenzofural group, 6 benzofural group, 7 benzofural group, 1 isobenzozofural group, 3-isobenzofural group, 4 isobenzozofural group Group, 5-isobenzofural group, 6 isobenzozofural group, 7 isobenzofural 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 quinoxalinyl group, 5 quinolyl group Xylol group, 6 quinoxalinyl group, 1-strength rubazolyl group, 2--strength rubazolyl group, 3--strength rubazolyl group, 4-strength rubazolyl group, 9-strength rubazolyl group, 13 carboline 1 yl, j8-carboline-3 —Yil, j8—Carboline—4—Yel, j8—Carboline—5—Yel, 13 Carboline 6—Yel, j8—Carboline 7—Yil, j8—Carboline 6—Yel, 13—Carboline—9 1 phenanthridyl group, 2 phenanthridyl group, 3 phenanthridyl group, 4 phenanthridyl group, 6-phenanthridyl group, 7-phenanthridyl group, 8 phenanthridyl group, 9 phenanthridyl group -L group, 10 phenidyl rigid group, 1-ataridyl group, 2-ataridyl group, 3-ataridyl group, 4-ataridyl group, 9-ataridyl group, 1,7 phenanthroline — 2—yl group, 1, 7 phenance Mouth phosphorus—3-yl group, 1,7 phenanthroline—4-yl group, 1,7 phenanthroline—5 —yl group, 1,7 phenanthroline—6-yl group, 1,7 phenanthroline—8— 1, 7 phenanthroline—9—yl group, 1, 7 phenanthroline—10—yl group, 1, 8 —phenanthroline 1—2-yl group, 1, 8 phenanthroline 1—3-yl group, 1, 8-phenanthroline 4-yl group, 1,8 phenanthroline 5-yl group, 1,8 phenanthroline 6-yl group, 1,8 phenanthroline 7-yl group 1,8 phenanthroline 9- 1 group, 1, 8 phenanthroline 10-yl group, 1, 9 phenanthroline 2-yl group, 1, 9 phenanthroline 3-yl group, 1, 9 phenanthroline 4-yl group, 1 , 9 Phenanthroline—5-yl group, 1, 9 Phenanthroline—6-yl group, 1, 9 Phenol Thsuloline—7—yl group, 1, 9 phenanthroline—8—yl group, 1, 9 phenanthroline—10 —yl group, 1,10 phenanthroline—2-—yl group, 1,10 phenanthroline—3— 1, 10-phenanthroline 4-yl group, 1, 10-phenanthroline 5-yl group, 2, 9 phenanthroline 1-yl group, 2, 9 phenanthroline 1-yl group, 2 , 9 Phenanthroline—4-yl group, 2, 9 Phenanthroline—5--yl group, 2, 9 Phenol-thrin 6—yl group, 2, 9 Phenanthroline-one 7-yl group, 2, 9 Phenanthroline 1 8 —yl, 2, 9 phenanthroline— 10—yl, 2, 8 phenanthroline— 1—yl, 2, 8 phenanthroline 3 —yl, 2, 8 phenanthroline 4 Group, 2, 8 —phenanthroline 5—yl group, 2, 8 phenanthroline 6—yl , 2, 8 Fuena Nsurorin one 7-I group, 2, 8 Fuenansurorin one 9-I group, 2, 8 Fuenansurorin — 10—yl group, 2, 7 phenanthroline 1—yl group, 2, 7 phenanthroline 1—yl group, 2, 7 phenanthroline 1—yl group, 2, 7 phenanthroline 1—yl group 2, 7 phenanthroline 6-yl group, 2, 7 phenanthroline 8-yl group, 2, 7 phenanthroline 9-yl group, 2, 7 phenanthroline 10-yl group, 1 phenadyl group, 2 phenadyl group Group, 1 phenothiazyl group, 2 phenothiazyl group, 3 phenothiazyl group, 4 phenothiazyl group, 10 phenothiazyl group, 1-phenoxazinyl group, 2 phenoxazyl group, 3 phenoxazyl group Group, 4 phenoxazyl group, 10 phenoxazyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2 oxaziazolyl group, 5 oxadiazolyl group, 3 flazanyl group, 2 chael group, 3 chael 2-methyl pyrrole 1-yl group, 2-methyl pyrrole 3-yl group, 2-methyl pyrrole 4-yl group, 2-methyl pyrrole 5-yl group, 3-methyl pyrrole 1-yl group, 3-methyl pyrrole 1-l group 2-yl group, 3-methyl pyrrole 4-yl group, 3-methyl pyrrole 5-yl group, 2 t-butyl pyrrole 4-yl group, 3-(2 phenylpropyl) pyrrole 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, 2 t-butyl 3 indolyl group, 4 Examples include t-butyl 3-indolyl group, pyrrolidine, virazolidine, piperidine, and the like.

Among these, 2-pyridyl group, 1-indolidyl group, 2-indolidyl group, 3-indolidyl group, 5-indolidyl group, 6-indolidyl group, 7 —Indolizyl group, 8 Indolizyl group, 2 Imidazopyridyl group, 3 Imidazopyridinyl group, 5 Imidazopyridinyl group, 6—Imidazopyridyl group, 7—Imidazopyridyl group, 8—Imidazopyridyl group Group, 3-pyridyl group, 4 pyridyl 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 -strength rubazolyl group, 3 -strength rubazo A ryl group, a 4-strength rubazolyl group, and a 9-carbazolyl group. [0045] The alkoxy group and Ariruokishi group is a group represented by OX ^1, is an example of X ^1, same examples as those described for the alkyl group and Nono Rogeni spoon alkyl and Ariru group Is mentioned.

The alkylamino group and the arylamino group are groups represented by —ΝΧ ^ ² , and examples of X ¹ and X ² are those described for the alkyl group, the halogenated alkyl group, and the aryl group, respectively. Similar examples are given.

Examples of the carboxyl-containing group include methyl ester, ethyl ester, and butyester.

Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a butyldimethylsilyl group, and a propyldimethylsilyl group.

Examples of the arylsilyl group include a triphenylsilyl group, a phenyldimethylsilyl group, and a t-butyldiphenylsilyl group.

Examples of the ring structure formed by crosslinking R ¹ and R ² include the same examples as those given for the heterocyclic group.

In general formula (1), when k is plural,

A ring and B ring may be the same or different, and may be bridged with each other.

[0047] Further, the compound power represented by the general formula (1) is preferably a transition metal complex compound having a metal carbene bond represented by the following general formula (2).

[Chemical 11]

In the general formula (2), C (carbon atom) → M represents a metal carbene bond.

M and k are the same as described above, m is an integer of 0 to 2, and k + m represents the valence of metal M. The

In the general formula (2), R ^{3 to} R ¹⁷ each independently represent a hydrogen atom, a halogen atom, a thiociano group, a cyano group, a nitro group, an —S (= 0) R ¹⁸ group, an —S (= 0) R ¹⁸ [R ¹⁸ is the same as above]

2

An alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, and a substituent. -30 aromatic hydrocarbon group, optionally substituted cycloalkyl group having 3 to 30 carbon atoms, cycloalkyl group having 7 to 40 carbon atoms, aralkyl group having 7 to 40 carbon atoms and substituents. May have an alkenyl group having 2 to 30 carbon atoms, a heterocyclic group having 3 to 30 nuclear atoms which may have a substituent, or a substituent, V, 1 to 30 carbon atoms May have an alkoxy group or a substituent, an aryloxy group having 6 to 30 nuclear carbon atoms, an alkylamino group having 3 to 30 nuclear atoms which may have a substituent, or a substituent. In addition, an arylaryl group having 6 to 30 carbon atoms, which may have a substituent, an alkylsilyl group having 3 to 30 nuclear atoms, an arylylsilyl group having 6 to 30 carbon atoms which may have a substituent, carbon It is a carboxyl-containing group having a number of 1 to 30, and R ^{3 to} R ¹⁷ may be adjacently crosslinked. /. Specific examples of these groups include the same examples as R ¹ and R ^{2 in} the general formula (1). The M is preferably Ir.

Next, general formula (3) will be described.

[Chemical 12]

In the general formula (3), C (carbon atom) → M represents a metal carbene bond, and the bond indicated by an arrow (→) represents a coordination bond. M is the same as described above, and Ir is preferable.

In the general formula (3), L ² represents a monodentate ligand. j is the same as above, and when j is plural, each L ² may be the same or different and may be cross-linked. In the general formula (3), L ² is the same ligand as described above, and the same specific examples can be given. In the general formula (3), L ³ is a super strong acid having a pKa value of −10 or less, Examples include carboxylic acids, aldehydes, ketones, alcohols, thioalcohols, phenols, amines, amides, aromatic or alkane conjugate bases, hydrogen ions, halide ions, and pKa values. — Conjugated bases and halides of super strong acids that are 10 or less are preferred.

As the conjugate bases of super strong acids whose pKa value is -10 or less, SbF-, FSO-, CIO

6 3 1, Γ, TfO—, Tf N "(Tf-= CF SO-) etc. are R as the conjugate bases of carboxylic acids.

4 2 3 2

COO—, ArCOO—Isotropic R COH as the conjugate base of aldehydes, R—COR ′ etc. as the conjugate base of ketones, RO—Isotropic thioalcohol conjugates as the conjugate base of alcohols As the base, RSO—Isotropic As the conjugate base of phenols, Ar O— etc. As the conjugate base of amamines, RR 'N—Issue As conjugated bases of amides, RR' NCOR "" isosity Examples of aromatic conjugate bases include (substituted) cyclopentadenyl-one, Ar—, and examples of alkane conjugate bases include Me—, tBu— (Me is methane, Bu is butane), and the like. As halide ions,

F-, Cl-, Br-, Γ.

Examples of R ′ and R ″ include the same examples as R ¹⁸ described above.

In the general formula (3), specific examples of L ³ -L ² (ligands in which L ³ and L ² are bridged) include, for example, conjugate bases of (substituted) acetylethylacetones, conjugate bases of j8 ketoimines Conjugated bases of j8 diimines, conjugated bases of (substituted) picolinic acid, conjugated bases of (substituted) malonic acid diesters, conjugated bases of (substituted) acetoacetic esters, conjugated bases of (substituted) acetoacetamides, (Substituted) conjugate bases of amidinates and the like.

In the general formula (3), Z ¹ is a carbon, silicon, nitrogen or phosphorus atom,

Z ³ and R ¹ are the same as those described above, and specific examples are the same.

In the general formula (3), specific examples of the A ring containing R ¹ Z ¹ and Z ² and the B ring containing Z ³ include the same examples as in the general formula (1).

Also,

A ring and B ring may be the same or different. It may be, or it may be cross-linked between adjacent ones.

Next, general formula (4) will be described.

[Chemical 13]

[0053] In the general formula (4), C (carbon atom) → M represents a metal carbene bond, a bond indicated by a solid line (-) represents a covalent bond, and a bond indicated by an arrow (→) represents a coordinate bond. means. M is the same as described above, and L ² represents a monodentate ligand. j is the same as above, and when j is plural, each L ² may be the same or different and may be cross-linked.

L ² is the same ligand as defined above, L ³ ,

Zeta ³ and R ^1, Ri same der as defined above, a similar embodiment can be mentioned.

In the general formula (4), specific examples of the A ring containing R ¹ Z ¹ and Z ² and the B ring containing Z ³ include the same examples as in the general formula (1).

Further, L ³ - Examples of L ² include the same examples as (L ³ and L ² are ligands crosslinked). Also,

The A ring and the B ring may be the same or different, and may be bridged with each other.

[0054] The method for producing the transition metal compound having a metal carbene bond represented by the general formula (7) of the present invention is represented by the iridium compound represented by the following general formula (5) and the following general formula (6). The imidazolium salt thus produced is reacted in the presence of a solvent and a base to produce a transition metal compound represented by the general formula (7).

[0055] [Chemical 14]

[0056] In the general formulas (5 to 7), C (carbon atom) → Ir (iridium) represents a metal carbene bond, a bond indicated by a solid line (one) represents a covalent bond, and an arrow (→) The bond shown by means a coordination bond. L ² represents a monodentate ligand. j is the same as described above, and when j is plural, each L ² may be the same or different and may be cross-linked.

L ² is the same ligand as defined above, L ³ ,

Rings A and B may be the same or different and may be bridged by adjacent ones.

In this production method, the solvent includes (substituted) aromatic hydrocarbons, (substituted) heteroatom-containing aromatics, (substituted) straight chain monoters, (substituted) cyclic cages. Ters, (substituted) cyclic thioethers, (substituted) alcohols, (substituted) aliphatic hydrocarbons, and the like. Specific examples of the (substituted) aromatic hydrocarbon include benzene, toluene, xylene, mesitylene, 1,2,3,4-tetrahydronaphthalene, and the (substituted) hetero atom-containing aromatic includes Pyridine derivatives such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, quinoline, isoquinoline, furan, 2-methyl Examples include furan derivatives such as tilfuran, 3-methylfuran, 2,5 dimethylfuran, and benzofuran, thiophene derivatives such as thiophene, 2-methylthiophene, 3-methylthiophene, 2,5 dimethylthiophene, and benzothiophene. Examples of linear ethers include diisopropyl ether, dibutyl ether, and diethylene glycol diethyl ether. Examples of (substituted) cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and 2,5 dimethyltetrahydrofuran. And tetrahydrofuran derivatives such as 2, 2, 5, 5-tetramethyltetrahydrofuran, and (substituted) cyclic thioethers include tetrahydrothiophene, 2-methyltetrahydrothiophene, 3-methyltetrahydride. Examples include tetrahydrothiophene derivatives such as thiophene, 2,5 dimethyltetrahydrothiophene, 2,2,5,5-tetramethyltetrahydrothiophene, and (substituted) alcohols include 2-methoxyethanol, diethyleneglycol , Tetrahydrofurfuryl alcohol, 1,4 butanediol, 1,6 hexanediol, glycerol, etc. (Substituted) aliphatic hydrocarbons include n decane, n dodecane, n-undecane, decalin, etc. It is done. Among these, (substituted) cyclic ethers, (substituted) alcohols, and (substituted) cyclic ethers, which are preferred (substituted) cyclic ethers, (substituted) tetrahydrofuran are more preferred.

As the base, an acid dissociation constant (pKa value) of 8 or more, preferably 15 or more, more preferably 15 or more and 40 or less, a compound having a combination force of a metal conjugate base and a metal, or a basic oxide The metal oxide which is is mentioned. Examples of the acid conjugate base having an acid dissociation constant (pKa value) of 15 or more and 40 or less include alkoxyadonone, acid amide aon, amide, alkylamido aon, arylamido aon and the like. Examples of alkoxy door-on include methoxy door-on, ethoxy door-on, etc., and examples of acid amido-on include benzoic acid amide-on, acetic acid amide-on, and the like. Examples of -on include methylamido-on and ethylamido-on. Examples of aryl-on include arylido-on. Examples of the metal to be combined with these conjugated bases include lithium cation, sodium cation, potassium cation and magnesium cation. Examples of the metal oxide that is a basic oxide include magnesium oxide, lithium oxide, acid sodium, acid calcium, copper oxide, and silver oxide. Acid silver is preferred.

[0058] Examples of the substituent of each group in the general formulas (1) to (7) include a substituted or unsubstituted aryl group having 5 to 50 nuclear carbon atoms and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. Substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl groups having 6 to 50 nuclear carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 50 nuclear carbon atoms, substituted or unsubstituted Examples thereof include aryloxy groups having 5 to 50 nuclear carbon atoms, substituted or unsubstituted alkoxycarbon groups having 1 to 50 carbon atoms, amino groups, halogen atoms, cyano groups, nitro groups, hydroxyl groups, and carboxyl groups. .

Among these, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms, and 5 to 7 carbon atoms are preferable. Cycloalkyl groups are more preferred methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl Particularly preferred is the cyclohexyl group.

[0059] As a specific example of the transition metal complex compound of the present invention, in the following general formula (8), the part containing the A ring and the part containing the B ring are the examples described above, respectively. However, it is not limited to these.

[Chemical 15]

Next, as a representative example of the method for producing a transition metal complex compound of the present invention, in the general formula (2), (i) M is an iridium atom, k = 3, m = 0, and (ii) M is iridium. The following synthesis route shows the production of atoms, k = 1, m = 2.

In the following synthesis route, the synthesis of the ligand is described in References (J. Am. Chem. Soc, 127 (10), 3290 -3291, 2005), and the following X represents a leaving group such as a halogen atom.

[Chemical 16]

Further, as a specific example of the general formula (1), it is shown in the following synthesis route of transition metal compounds, where acac is acetylylacetonate.

[Chemical 17]

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 also having an anode and a cathode force. Contains a transition metal complex compound represented by at least one of the general formulas (1), (3) and (4) of the present invention and represented by the general formula (3) and Z or (4). Containing transition metal complex compounds.

The content of the metal complex compound of the present invention in the organic thin film layer is usually 0.1 to L00% by weight and preferably 1 to 30% by weight with respect to the total mass of the light emitting layer. .

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. In general, the light emitting layer can be made thin by vacuum deposition or coating. Since the coating process can simplify the manufacturing process, the layer containing the transition metal complex compound of the present invention is formed by coating. This is preferable. In the organic EL device of the present invention, when the organic thin film layer is of 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. Also many As a layer type organic EL device, (Anode Z Hole injection layer (Hole transport layer) Z Light emitting layer Z Cathode)

(Anode Z light-emitting layer Z Electron injection layer (electron transport layer) Z cathode), (Anode Z hole injection layer (hole transport layer) Z light-emitting layer Z electron injection layer (electron transport layer) Z cathode), etc. It is done.

[0064] 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 is effective to have a work function of 4.5 eV or more. is there. 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, indium tin oxide (ITO), or metals such as gold, silver, chromium, nickel, and conductive materials thereof. Mixture or laminate of conductive metal oxide and metal

Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyarlin, polythiophene and polypyrrole, and laminates of these with ITO, preferably conductive metal oxide In particular, it is preferable to use ITO in view of productivity, high conductivity, transparency, etc. The film thickness of the anode can be appropriately selected depending on the material.

[0065] 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. Examples of the cathode material include metals, alloys, metal halides, metal oxides. , Electrically conductive compounds, or mixtures thereof. 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 such as indium and ytterbium And the like. Of these, aluminum and lithium-aluminum are preferable.

-Um alloy or lithium-aluminum mixed metal, magnesium-silver alloy or magnesium-silver mixed metal. 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 Z lithium fluoride and aluminum / lithium oxide is preferable. The film thickness of the cathode can be appropriately selected depending on the material.

[0066] The hole injection layer and the hole transport layer of the organic EL device of the present invention inject holes from the anode. Any one having a function, a function of transporting holes, or a function of blocking the injected electrons from the cathode can be used. Specific examples thereof include strength rubazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine amines, 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-butylcarbazole) derivatives And electropolymer oligomers such as alkylen-based copolymers, thiophene oligomers and polythiophenes, organic silane derivatives, and transition metal complex compounds of the present invention. In addition, 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 having a multi-layer force of the same composition or different compositions. It may be.

[0067] The electron injection layer and the electron transport layer of the organic EL device of the present invention have any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. What is necessary is just to have. Specific examples thereof include triazole derivatives, oxazol derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carpositimide derivatives, fluorenylidenemethane derivatives. , Metal complexes of aromatic ring tetracarboxylic acid anhydrides such as distyrylvirazine derivatives, naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole and benzothiazole as ligands. Examples include various metal complexes, organosilane derivatives, and transition metal complex compounds of the present invention. In addition, 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 having a multi-layer force of the same composition or different compositions. Moyo.

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

[Chemical 18]

[0069] [Chemical 19]

[0070] [Chemical 20]

In the organic EL device of the present invention, it is preferable that the electron injection layer and the Z or electron transport layer contain a π electron deficient nitrogen-containing heterocyclic derivative as a main component.

As the π-electron deficient nitrogen-containing hetero ring derivative, a nitrogen-containing 5-membered ring derivative selected from benzimidazole ring, benztriazole ring, pyridinoimidazole ring, pyrimidinoimidazole ring, pyridazinoimidazole ring, A nitrogen-containing 6-membered ring derivative composed of a pyridine ring, a pyrimidine ring, a pyrazine ring, or a triazine ring is preferred. Preferred examples of the nitrogen-containing 6-membered ring derivative include structures represented by the following general formulas C—I, c—n, c—m, C—IV, Ji and Hide- ^, and particularly preferred. Is a structure represented by general formulas CI and C-II. [0072] [Chemical 21]

(B— I)

In the general formula (B- I), L ^B represents a divalent or higher linking group, preferably carbon, Keimoto, nitrogen, boron, oxygen, sulfur, metals, a linking group formed like a metal ion More preferably a carbon atom, a nitrogen atom, a carbon atom, a boron atom, an oxygen atom, a sulfur atom, an aromatic hydrocarbon ring or an aromatic heterocycle, and still more preferably a carbon atom, a carbon atom or an aromatic. It is a hydrocarbon ring or an aromatic hetero ring.

[0073] L ^B is preferably an alkyl group as Yogu substituent may have a substituent, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an amino group, an alkoxy group, Ariruokishi group, § sill group, an alkoxy Carbon group, aryloxycarbol group, acyloxy group, acylamino group, alkoxy carbolumino group, aryloxycarbolamino group, sulfo-lumino group, sulfamoyl group, rubamoyl group, alkylthio Group, aryl group, sulfonyl group, halogen atom, cyano group and aromatic heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, halogen atom, cyan group and aromatic heterocyclic group. More preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an aromatic heterocyclic group. Particularly preferably an alkyl group, Ariru group, an alkoxy group, an aromatic heterocyclic group.

[0074] include those of the following specific examples of the linking group represented by L ^B.

[Chemical 22]

-C- "Si—" Ge- ^ N ^ P \

In the general formula (B—I), X represents —O—, —S— or = N—R. R 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, particularly preferably 1 to 8 carbon atoms). For example, methyl group, ethyl group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. ), A alkenyl group (preferably a alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. Group, 2-buture group, 3-pentane group, etc.), alkyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms). Alkynyl groups such as propargyl group, 3-pentynyl Etc. can be mentioned, et al are.), More preferably an alkyl group.

The aryl group represented by R ^B2 is a monocyclic or condensed aryl group, preferably having 6 to 6 carbon atoms. 30, more preferably an aryl group having 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms, such as a phenyl group, a 2-methylphenol group, a 3-methylphenol group, a 4-methylphenol group, Examples include 2-methoxyphenyl group, 3-trifluoromethylphenol group, pentafluorophenyl group, 1-naphthyl group, 2-naphthyl group.

[0076] The heterocyclic group represented by R ^B2 is a monocyclic or condensed heterocyclic group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 2 to 10 carbon atoms). Heteroaromatic group, 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, pteridine, Ataridine, phenanthorin, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene, carbazole, azepine and the like are preferable, and furan, thiophene, pyridine, virazine, pyrimidine are preferable. , Pyridazine, triazine, quinoline, phthalazine, naphthyridine, quinoxaline, and quinazoline, more preferably furan, thiophene, pyridine, and quinoline, and more preferably quinoline.

Aliphatic hydrocarbon group represented by R ^B2, Ariru group, heterocyclic group include the same device it may also have a substituent wherein L ^B.

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.

[0077] X ⁸² is preferably Ο—, = Ν—R ^B2 , more preferably = N—R ^B2 , particularly preferably = N—Ar ^B2 (Ar ^B2 is an aryl group (preferably 6-30 carbon atoms, more preferably 6-20 carbon atoms, still more preferably 6-12 carbon aryl groups, and aromatic heterocyclic groups (preferably 1-20 carbon atoms, more preferably 1-carbon atoms). 12, more preferably an aromatic heterocyclic group having 2 to 10 carbon atoms, and preferably an aryl group).

[0078] Z ^B2 represents an atomic group necessary for forming an aromatic ring. The aromatic ring formed by Z ^B2 is Specific examples of the aromatic hydrocarbon ring and the aromatic heterocycle include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a furan ring, and a thiophene ring. Selenophene ring, terorophene ring, imidazole ring, thiazole ring, selenazole ring, tellurazole ring, thiadiazole ring, oxadiazole ring, pyrazole ring, etc., preferably benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, A pyridazine ring, more preferably a benzene ring, a pyridine ring, or a pyrazine ring.

More preferred are a benzene ring and a pyridine ring, and particularly preferred is a pyridine ring. The aromatic ring formed by z ^B ² may further form a condensed ring with another ring or may have a substituent. As a substituent, preferably an alkyl group, an alkyl group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, an acyloxy group. Group, acylamino group, alkoxy carbo-lumino group, aryloxy carbo-lumino group, sulfo-lumino group, sulfamoyl group, strong rubamoyl group, alkylthio group, arylothio group, sulfol group, halogen atom, cyano group A heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, or a heterocyclic group, and even more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group. Group, aromatic heterocyclic group, particularly preferably alkyl group, aryl group, alkoxy group. Group, Ru heterocyclic group der aromatic.

n ^B2 is an integer of 1 to 4, preferably 2 to 3.

Among the compounds represented by the general formula (B-I), a compound represented by the following general formula (B-II) is more preferable.

[Chemical 23] (B -II)

In general formula (B-II), R ^B71 , R ^B72 and R ^B73 are the same as R ^B2 in general formula (BI), respectively, and the preferred ranges are also the same.

Z ^B72 and Zeta ^Beta73 are similar to Zeta ^B2 in the general formula (Beta iota) respectively, also are similar ranges have preferred.

L ^B71, L ^B72 and L ^B73 each represent a linking group, the general formula (B- I) can be mentioned those divalent examples of L ^B in, preferably, a single bond, a divalent aromatic hydrocarbon A hydrogen ring group, a divalent aromatic heterocyclic group, and a linking group having a combination force thereof, more preferably a single bond. L ^m , L ^B72 and L ^B73 may have a substituent. Examples of the substituent may be the same as L ^{B in the} general formula (BI).

Y represents a nitrogen atom, a 1, 3, 5-benzenetriyl group or a 2, 4, 6-triazine triyl group. The 1, 3, 5-benzenetriyl group may have a substituent at the 2, 4, 6-position, and examples thereof include an alkyl group, an aromatic hydrocarbon ring group, and a halogen atom. It is possible.

Specific examples of the nitrogen-containing five-membered ring derivative represented by the general formula (B-I) or (B-II) are shown below. The power is not limited to these exemplified compounds.

[Chemical 24]

ШЩωΒι

(Cz-) nA (C—I)

Cz (-A) m (C-II)

[Wherein, Cz is a substituted or unsubstituted carbazolyl group, aryl carbazolyl group or force rubazolylalkylene group, and A is a group formed from a site represented by the following general formula (A). n and m are integers from 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 ' Can be the same or different. L is a single bond, an arylene group having 6 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or a heteroaromatic ring having 2 to 30 carbon atoms, and having a substituent bonded to the ring. May not be included. p is an integer from 0 to 2, q is an integer from 1 to 2, and r is an integer from 0 to 2. However, p + r is 1 or more. ]

[0084] The coupling mode of the general formulas (C-1I) and (C-1II) is specifically represented by the number of parameters n and m as shown in the following table.

[table 1]

[0085] In addition, the bonding mode of the group represented by the general formula (A) depends on the number of parameters p, q, r, specifically, the forms described in (1) to (16) in the following table. It is.

[Table 2]

[Table 3]

In the general formulas (C I) and (C II), when Cz is bonded to A, it may be bonded to any part of M, L, and M ′ representing A. For example, in Cz—A where m = n = l, if p = q = r = l ((6) in the table), A becomes M—L—M, and Cz—M—L—Μ ', M— L (—Cz) —M ′ and M—L—M′—Cz. Similarly, in Cz—A—Cz where, for example, in the general formula (C-1), n = 2, p = q = l, r = 2 (in the case of (7) in the table, A is ML -M'-M 'or M-L (Μ')-M.

[0087] [Chemical 26]

Cz-M-L-M'-M 'Cz- M- -M'-M' Cz- M-L-M'-M '

I I

Cz Cz Cz

Cz

I

Cz- M-L-M'-M'- Cz, M-L-M'-M 'M-L-M'-M'

I I I

Cz Cz Cz

Cz

I

ML-M'-M ' ¹ Cz ML-M'-M' ML- M'-M'- Cz

I I

Cz Cz Cz

M- -M '

Cz Cz

M-vL-M '

M '

Specific examples represented by the general formulas (C I) and (C II) are not limited to these examples.

[Chemical 27]

[0089] [Chemical 28]

(C- I I I)

(In the formula, Ar to Ar each represent the same group as R ^{B2 in the} general formula (B—I), and specific examples thereof are also the same.

11 13

Ar to Ar represent divalent groups similar to R ^{B2 in} the general formula (B—I).

13

The example is similar. )

Specific examples of the general formula (C-III) are shown below, but are not limited thereto.

[Chemical 29]

[0090] [Chemical 30]

(Wherein R to R each represent the same group as R ^{B2 in the} general formula (B—I), and specific examples thereof are also the same)

11 14

It is. )

Specific examples of the general formula (C—IV) are shown below, but are not limited thereto.

[Chemical 31]

[Chemical 32]

(cv)

(In the formula, ： ι: ¹ to Ar ³ each represent the same group as R ^{B2 in the} general formula (BI), and specific examples thereof are also the same.)

Specific examples of the general formula (C—V) are shown below, but are not limited thereto.

[Chemical 33]

[Chemical 34]

(C-VI)

(In the formula, Ai: ¹ to Ar ⁴ are the same groups as R ^{B2 in the} general formula (B—I), and specific examples are also the same) It is. )

Specific examples of the general formula (CVI) are shown below, but are not limited thereto.

[Chemical 35]

[0093] Further, 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 injection / transport layer is composed of an insulator or a semiconductor, current leakage can be effectively prevented and electron injection 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, alkali 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, preferred alkali metal chalcogenides include, for example, Li 0, LiO, Na

twenty two

S, Na Se and NaO are mentioned, and preferred alkaline earth metal chalcogenides include

2

Examples thereof include CaO, BaO, SrO, BeO, BaS, and CaSe. Preferred examples of the alkali metal halide include LiF, NaF, KF, LiCl, KC1, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as Ca F, BaF, SrF, MgF and BeF, and halides other than fluorides.

2 2 2 2 2

Things.

[0094] Further, as a semiconductor constituting the electron injection 'transport layer, at least one of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn is used. One or a combination of two or more of oxides, nitrides, and oxynitrides containing elements can be used. In addition, the inorganic compound constituting the electron transport layer is preferably a microcrystalline or amorphous insulating thin film. If the electron transport layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include the alkali metal chalcogenides and alkaline earths described above. Metal halide chalcogenides, alkali metal halides and alkaline earth metal halides.

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.

[0095] Further, in the present invention, at least a part of the organic layer contained in the interface region that is preferred when the reducing dopant is added to the interface region between the cathode and the organic thin film layer is reduced. Turn on. 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 oxide, alkali It is at least one compound selected from the group consisting of earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes. More specifically, preferred 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 95eV) Force Group Force At least one selected alkali metal, Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV) and Ba (work function: 2.52 eV) Powerful group power At least one alkaline earth metal selected is mentioned, and a work function of 2.9 eV is particularly preferred. 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 can improve emission brightness and extend the life of organic EL devices by adding a relatively small amount to the electron injection region, which has a particularly high reducing ability.

[0096] Examples of the alkaline earth metal oxides include BaO, SrO, CaO and Ba Sr O (0 <x <1) mixed with these and Ba Ca O (0 <x <1). Are listed as preferred

1 1

be able to. Examples of alkali oxides or alkali fluorides include LiF, Li 0, and NaF.

2

I can get lost. 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 quino Linol, benzoquinolinol, attaridinol, phenanthridinol, hydroxyphenyl thiazole, hydroxyphenyl thiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylvinylidine, hydroxyphenylbenzo Imidazole, hydroxybenzotriazole, hydroxyfulborane, bipyridyl

Force including, but not limited to, phenanthrin, phthalocyanine, porphyrin, cyclopentagen, 13-diketones, azomethines, and derivatives thereof.

[0097] Further, as a preferred form of the reducing dopant, it is formed in a layer shape or an island shape. The preferred film thickness is 0.05 to 8 nm.

As a method for forming an electron injecting / transporting layer containing a reducing dopant, an organic substance that is a light-emitting material or an electron injecting material that forms an interface region is simultaneously deposited while a reducing dopant is deposited by resistance heating vapor deposition. A method in which a reducing dopant is dispersed therein is preferred. 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 alone by resistance heating evaporation, preferably 0.5 nm in thickness. ηπ! Form at ~ 15nm. When forming the reducing dopant in the form of an island, 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 evaporation method, preferably 0.05 to ln. Form with m.

[0098] 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. It provides a function to move the generated charges (electrons 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 may contain a host material using the transition metal complex compound as a guest material, which preferably contains at least the transition metal complex compound of the present invention. Examples of the host material include those having a force rubazole 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 allylsilane skeleton. . T1 (minimum triple) of the host material The energy level of the excited state is preferably greater than the T1 level of the guest material. The host material may be a low molecular compound or a high molecular compound. In addition, by co-evaporating the host material and the light emitting material such as the transition 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, a 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, and the like. 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 preferred.

In addition, the organic thin film layer containing the transition metal complex compound of the present invention can be prepared by vacuum deposition, molecular beam deposition (MBE), solution dating, solvent coating, spin coating, casting, bar coating. It can be formed by a known method using a coating method such as a coating method or a roll coating method.

The coating method can be formed by dissolving the transition metal complex compound of the present invention in a solvent to prepare a coating solution, and coating and drying the coating solution on a desired layer (or electrode). . In the coating solution, rosin which may contain rosin 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 polymer) can be used. More specifically, for example, poly (vinyl chloride), polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfonate, polyphenoloxide, polybutadiene, poly (N-butylcarbazole), Hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, butyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin Examples include fats.

In addition, the thickness of each organic layer of the organic EL element of the present invention is not particularly limited. In general, however, if the film thickness is too thin, defects such as pinholes are generated. Usually, the range of several nm to 1 μm is preferable because of worsening. Example

Next, the present invention will be described in more detail using examples.

Example 1 (Synthesis of Transition Metal Complex Compound 1)

(i) Synthesis of compound a

In the following reaction process, compound a was synthesized according to the method described in the reference (Chem. Pharm. Bull., 1965, 13, 1135).

[Chemical 36]

[0101] In an eggplant flask, 25.6 g (0.239 mol) of 2-pyridinemethanol, 20.3 milliliters of phosphorus (0.214 monole), and 1.92 g of potassium hydroxide (0. 0341) Monole), 150. The mixture was heated and stirred at C for 12 hours. As a result, it changed from a pale yellow oil state to a pale yellow suspended state. This was cooled to room temperature, 200 ml of water was added, and neutralized with dilute hydrochloric acid until the pH reached about 7-8. Next, 500 ml of methylene chloride was added to the reaction solution, and the organic layer was extracted using a separatory funnel. Further, extraction was performed 4 times with 100 ml of methylene chloride. This solution was dehydrated with potassium carbonate, solid components were filtered off, and the solvent was distilled off under reduced pressure to obtain a tan pasty solid. Distillation under reduced pressure from this pasty solid gave 7.70 g (0.0417 mol, yield 18%) of a red-orange oil. The distillation temperature was 115 ° C in ImmHg. As a result of measuring ¹ H-NMR of this red-orange oil, it was found that the main component was the target compound a.

^ H—NMR (apparatus: instrument name Varian MERCURY 300> 3OOMHz, solvent: deuterated chloroform, internal standard: TMSO. 00ppm, temperature: 35.C): 6 4. 45 (s, 2H, CH), 6 4 . 73 (

2

br, 1H, ΝΗ), δ 6. 65— 7. 24 (m, 5H, benzene ring), δ 7. 18— 8. 58 (m, 4H

Pyridine ring)

[0102] (ii) Synthesis of compound b

Compound b was synthesized in the following reaction process. [Chemical 37]

[0103] Compound b was synthesized using compound a synthesized in (i) above. In the presence of Sichus, 2.82 g (0.0153 monole) of compound a and 2.90 milliliters of formic acid (0.007 65 mol, 5 equivalents) were added and stirred at 95 ° C for 4 hours. Was done. This was cooled to room temperature, 100 ml of water was removed, and extraction was performed with methylene chloride (5 times each in 50 ml). Magnesium sulfate was added to this solution for dehydration, the solid component was filtered off, and the solvent was distilled off under reduced pressure to obtain a brown oil. Next, as a result of purification by silica gel column chromatography (developing solvent: hexane Z ethyl acetate = 1Z1), 2.06 g of a dark reddish brown oil was obtained (yield 63%, Rf value 0.7). As a result of measuring ¹ H-NMR of this, it was found to be the target compound b.

^ H—NMR (apparatus name: Varian MERCURY 300> 3OOMHz, solvent: deuterated chloroform, internal standard: TMSO. 00ppm, temperature: 35.C): δ 5. 18 (s, 2H, CH), δ 7 . 14

2

-7. 38 (m, 5Η, benzene ring), δ 7. 14— 8. 54 (m, 4H, pyridine ring), δ 8. 65 (s, 1Η, aldehyde)

[Iii] (iii) Synthesis of compound c

Compound c was synthesized in the following reaction process.

[Chemical 38]

Compound c was synthesized using compound b synthesized in (ii) above. In an eggplant flask, put Compound B (1.03 g, 4.85 millimonoles), aged salted salt, 0.50 milliliter Nore (5.34 millimonoles), and 10 milliliters of toluene at 80 ° C for 12 hours. , Heated and stirred (divided into two layers) Released). This solution was distilled off under reduced pressure to obtain 1.97 g of a greenish gray solid as a crude product. 40 ml of methylene chloride was added to 0.602 g of this crude product, and after sufficient stirring, solid components were removed using a centrifugal separator to obtain a greenish brown solution. When this was concentrated to a volume of 5 ml, and 50 ml of jetyl ether was added with stirring, a pale green precipitate formed, which was separated and dried. — NMR and H—H COZY assigned a peak, which was found to be the desired product c (0.287 g yield 83%). Fig. 1 shows the measurement results of ^J H -N MR.

[0106] ^ H—NMR (device: device name Varian MERCURY 300> 3OOMHz, solvent: deuterated chloroform, internal standard: TMSO. 00ppm, temperature: 35.C): δ 7. 07 (dd, J = 7. 1, 6. 6Hz, 1 H, H ^c ), 7. 24 (dd, J = 9. 3, 6. 6Hz, 1H, H ^d ), 7. 56—7.84 (m, 5H, H ^{g, h, i), 7. 70} (d, J = 9. 3Hz, 1H, H e), 8. 09 (s, 1H, H f), 9. 14 (d, J = 7. 1Hz, 1H, H ^b ), 11.38 (s, 1H, H ^a )

[Chemical 39]

[Iv] (iv) Synthesis of compound d

In the following reaction process, compound d was synthesized _c

[Chemical 40]

Compound d

[(COD) IrCl] ((cyclooctadiene) in a 20 ml Schlenk tube under an argon stream.

2

N) Iridium chloride (dimer)) 0.154 g (0.229 mmol), KOt—Bu (tertiary butoxypotassium) 0.154 g (l. 37 mmol), solvent ethanol 5.0 ml And stirred at room temperature for 5 hours. Next, 0.211 g (0.915 mmol) of compound c was added and stirred at room temperature for 2 hours. Next, the solvent is distilled off under reduced pressure, the resulting red-orange solid is dissolved in methylene chloride, the white solid is filtered off, and the solvent is distilled off under reduced pressure of methylene chloride. 0.290 g (yield 87%) of (reddish orange solid) was obtained. Fig. 2 shows the NMR measurement results.

[0109] (V) Synthesis of transition metal complex (compound 1)

Compound 1 was synthesized through the following reaction steps.

[Chemical 41]

Compound 1

[0110] Under argon atmosphere, compound d (202 mg, 0.278 mmol), degassed 2-ethoxyethanol (15.0 ml) was placed in Schlenk, refluxed for 2 hours in an oil bath. It was. The solution also turned red-orange to a brown suspension.

After cooling to room temperature, calorie potassium tertiary butoxide was charged with 187 mg (1.67 mmol), stirred for 3 hours at room temperature, then compound C was added with 128 mg (0.555 mmol), and a reflux tube was attached to the oil. The bath was refluxed for 2 hours. The solution became a brown suspension with a slightly reddish color.

After the solvent was distilled off under reduced pressure, column chromatography (developing solution: methyl chloride: Rf value 0.91) was performed in an air atmosphere. 3 5.2 mg (yield 16.4%) was obtained.

The solvent was further distilled off from the crude product, and the residue was purified by column chromatography using a degassed solvent (methylene chloride: hexane = 1: 1) under an argon atmosphere. Obtained in milligrams (yield 3.8%). The NMR measurement results are shown in FIG.

[0111] The following (1) to (3) were measured for the obtained composite under the same conditions as in Example 1. <Various measurement results>

(1) EI-MS measurement (electron ion mass spectrometry): The maximum peak value is 772, which matches the calculated value (M +) (calculated value M + = 772).

(2) NMR (300MHz) spectrum measurement: see Fig. 3

Equipment: Varian MERCURY 300

Measuring solvent: Solvent CD C1 (deuterated methylene chloride), standard 5.32ppm

twenty two

From the results of (1) and (2) above, the structure of Compound 1 was identified.

In addition, the emission spectrum of Compound 1 was measured (apparatus: spectrofluorophotometer Hitachi F—

4500, measurement solvent: methylene chloride), maximum emission wavelengths were observed at 388 nm, 409 nm, and 435 nm.

Example 2 (Synthesis of Transition Metal Complex Compound 1)

(i) Synthesis of compound e

Compound e was synthesized through the following reaction steps.

[Chemical 42]

Yield: Quantitative ¹ ^{Hira ¾le} eggplant flask [Tonolen 50 ml Lit Nore, 2 Pyridine canoleboxyanoredecht 9.55 ml (0. lOOmol, 1. Oeq), Alin 9.13 ml (0 lOOmol, 1. Oeq) was added and a light yellow solid was formed as soon as stirring was started. When the stirring was continued, all the solids dissolved and became a colorless solution. After stirring at room temperature for 24 hours, the solvent was distilled off under reduced pressure to quantitatively obtain a light yellow oily compound e. ¾-NMR measurement results are shown.

NMR (solvent: CDC1, internal standard: TMSO. OOppm, 300MHz, temperature: 35 ° C):

Three

δ 7. 28- 7. 45 (m, 5H, H ^Ph ), 7. 37 (ddd, J = 7. 7, 4. 7, 1. 1Hz, 1H, H), 7 b

82 (ddd, J = 7. 7, 7. 7, 1. 9Hz, 1H, H), 8. 21 (dd, J = 7. 7, 1. 9 Hz, 1H, H), 8. 62 ( s, 1H, H), 8. 72 (dd, J = 7. 7, 1. 1 Hz, 1H, H).

DEA

[Chemical 43]

[0114] (ii) Synthesis of Compound c

In the following reaction process, compound c was synthesized _c

[Chemical 44]

Compound. Yield: 18% Compound,

[0115] Compound el. 82 g (10. Ommol), finely pulverized granular paraformaldehyde (containing (CH 2 O), 91%) in an eggplant flask under Ar atmosphere 0. 328 g (12. Ommol), toluene 50

2 n

A milliliter was added and stirred at room temperature for 24 hours to completely dissolve (CH 2 O) in toluene.

2 n

Then, 2.8 ml (11. Ommol) of hydrochloric acid (4M, 1,4-dioxane solution) was added and stirred at room temperature for 1 day. Instantaneous force of adding hydrochloric acid solution A yellow solid started to precipitate.

The orange-brown solid obtained by distilling off the solvent under reduced pressure was filtered through Celite with CH C1, and the filtrate was filtered.

twenty two

Drying under reduced pressure gave a crude product as a yellow solid. This was recrystallized from hot acetone to purify pale yellowish brown compound c (0.41 lg, yield 18%).

¹ H-NMR and MS (FAB +) (FAB-MS: Fast electron impact mass spectrometry, instrument: FAB— MS: JEOL JMS— 700 Mass spectrometer (using 3-nitrobenzylalcohol as a matrix)) were measured. As a result, it was found to be the target compound e.

Compound. 'H-NMRCCDCl, 300MHZ, 35 ° C):

Three

δ 7. 07 (dd, J = 7. 1, 6. 6Hz, 1H, H ^c ), 7. 24 (dd, J = 9. 3, 6. 6Hz, 1H, H ^d ), 7. 56- 7.84 (m, 5H, H ^Ph ), 7.70 (d, J = 9.3 Hz, 1H, H °), 8. 09 (s, 1H, H ^f ), 9.14 (d, J = 7.1Hz, 1H, H ^b ), 11. 38 (s, 1H, H ^a ).

MS (FAB +): m / z = 195. 1 (M—CI—)

[Chemical 45]

[0116] (iii) Synthesis of Compound f

Compound f was synthesized in the following reaction process.

[Chem 46]

[0117] [(COD) IrCl] 672 mg (l. OOmmol), NaOMe 432 mg (8.

2

OOmmol), degassed 2-Ethoxyethanol 50ml was placed in Schlenk and stirred at room temperature for 2 hours (yellow solution). Then, ligand precursor compound c923mg (4.OOmmol) was added and a reflux tube was attached. The mixture was refluxed in an oil bath for 3 hours. The solution turned from a red-orange color to a brown suspension.

After distilling off the solvent under reduced pressure, column chromatography using degassed solvent (CH C1) · silica gel

twenty two

Purification was performed with GRAPHI. 676 mg (0.550 mmol, yield 55.0) of yellow solid product

%).

As a result of measuring ¹ H-NMR, ¹³ C-NMR and MS (FAB +) (FAB-MS: fast electron impact mass spectrum), it was found that it was the target compound f.

[0118] Compound f — NMR (CD CI, 300MHz, 25 ° C):

twenty two

™ 5.84 (d, J = 7.4Hz, 1H, H, 5.86 (dd, J =

7.1, 6.8Hz, 1H, H ^b ), 6.38 (dd, J = 7.4, 7.0, 1H, H ^h ), 6.60 (dd, J = 8.8, 6.8Hz, 1H, H ^c ), 6.78 ( dd, J = 7.4, 7. OHz, 1H, H ^g ), 7.21 (d, J = 8.8, Hz, 1H, H ^f ), 7.21 (d, J = 7.4, Hz, 1H, H ^d ), 7.82 (s, 1H, H °), 9. 18 (d , J = 7.1 Hz, 1H, H ^a ).

Compound f ¹³ C—NMR (CD CI, 75 MHz, 25 ° C.):

twenty two

™ 104. 2, 111. 1, 111. 9, 116. 9, 120. 8, 12

1. 4, 125. 2, 125. 3, 129. 7, 130. 7, 136.4, 146. 0, 165.4

MS (FAB ⁺ ): m / z = 1228.2 (M +)

Neusteine test: positive

(Beilshutein test: When a copper wire heated to a compound containing chlorine is attached to plastic, copper chloride is formed, and a blue-green flame reaction can be confirmed.)

(iv) Synthesis of transition metal complex (compound 1)

Compound 1 was synthesized through the following reaction steps.

[Chemical 47]

Compound f Compound 1

[0120] Under an argon atmosphere, Schlenk was charged with compound f 61.4 mg (0. 0500 mmol), silver (I) oxide (Ag O (l)) 139 mg (0. 600 mmol), compound c23. Lmg (0. lOOmmol) ), 2-methoxy

2

20 ml of ethanol (degassing solvent) was added, and the mixture was stirred for 24 hours at 120 ° C while being protected from light with aluminum foil. The resulting brown suspension was filtered through Celite (CH C1) under an argon atmosphere.

2 2 to remove residual Ag 0 and salty silver (AgCl), and further to a degassing solvent (methylene chloride (CH C1):

2 2 2 Xane = 1: 1) 'Purified by column chromatography using silica gel. The solvent was distilled off under reduced pressure to obtain 5. lmg (0.0063 mmol, yield 6.6%) of a pale yellow solid.

The results of iH-NMR measurement are shown in FIG. From the peak splitting pattern and the integral intensity ratio, the product is considered to be the mer body.

[0121] Example 3 (Synthesis of transition metal complex compound 1)

Compound 1 was synthesized through the following reaction steps.

[Chemical 48]

[0122] Under argon atmosphere, compound f 123mg (0. lOOmmol), silver oxide (I) (Ag

2

0 (l)) 278 mg (l.20 mmol), y compound c 50.7 mg (0.220 mmol), tetrahydrofuran (THF, degassed solvent) 20 ml were added, and the mixture was stirred for 24 hours under reflux while being protected from light with aluminum foil. The solvent component was distilled off from the reaction solution under reduced pressure, and this was degassed solvent (CH C1: hexane = 2).

twenty two

1) and purified by silica gel column chromatography. As a result, 82. lmg (0.114 mmol, yield 57.0%) of a pale yellow solid was obtained.

The results of cyclic voltammetry (see Fig. 5) and X-ray crystal structure analysis (see Fig. 6) are shown below.

[FAB—MS measurement results]

MS (FAB ⁺ ): m / z = 772 (M ⁺ ), 579 (M + — (Ligand))

[Cyclic voltammetry measurement results (vs Ag + ZAg in CHQ, apparatus: HOKUTOD

twenty two

ENKO HSV-100)]

E ^ox = 0.35, E ^RED = — 1.33 (V)

[0123] Example 4 (Synthesis of Transition Metal Complex Compound 2)

Compound 2 was synthesized by the following reaction process.

[Chemical 49]

Compound f Compound 2

Under an argon atmosphere, a Schlenk tube was charged with Compound f 123 mg (0.100 mmol), NaOMe 21.6 mg (0.400 mmol), Acetylacetone (acacH) O.04 ml (0.40 mmol), Te 20 ml of trahydrofuran (THF, degassed solvent) was added and stirred for 14 hours under reflux. The solvent component was distilled off from the reaction solution under reduced pressure to obtain a crude product (yellow solid). This was purified by silica gel chromatography (developing solvent: degassed methylene chloride). As a result, 86.2 mg (0.114 mmol, yield 63.9%) of a tan solid was obtained. The NMR results are shown below.

Compound f'H-NMRCCDCl, 300MHz, 35 ° C):

Three

δ 1.75 (s, 6H, CH), 5.20 (s, 1H, COCHCO),

Three

6.14 (dd, J = 7.4, 1.4Hz, 2H, H,

6.42 (ddd, J = 7.4, 6.3, 1.1Hz, 2H, H ^h ),

6.48 (ddd, J = 7.4, 7.4, 1.0Hz, 2H, H ^b ),

6.75 (ddd, J = 7.7, 7.4, 1.1Hz, 2H, H ^c ),

6.78 (ddd, J = 9.6, 6.3, 1.4, Hz, 2H, H ^g ),

7.17 (dd, J = 7.7, 1.0Hz, 2H, H ^d ),

7.34 (d, J = 9.6, 1.1Hz, 2H, H ^f ), 7.73 (s, 2 H, H °),

8.26 (dd, J = 7.4, 1. 1Hz, 2H, H a).

[Chemical 50]

[EI—MS measurement result]

MS (EI ⁺ ): m / z = 678.3 (M +), 579.2 (M + — (acac))

[Cyclic voltammetry measurement results (vs Ag + ZAg in CH CI)]

twenty two

E ^ox = 0.49, E ^RED = — 1.25 (V)

[Infrared absorption spectrum measurement results]

IR (KBr disc): v + v = 1581, v + v = 1518cm— ¹ (Device: Jasco F

(c = c) (c = o) (c = c) (c = o)

T / IR-410)

¾—NMR results (see Fig. 7), cyclic voltammetry results (see Fig. 8) and X-rays The results of crystal structure analysis (see Fig. 9) are shown.

Example 5 (Synthesis of Transition Metal Complex Compound 3)

Compound 3 was synthesized in the following reaction process.

(i) Synthesis of compound g

[Chemical 51]

Yield: quantitative ^ftg

[0128] Toluene 50 ml, 2-pyridinecarboxaldehyde 9.55 milliliters (0. lOOmol, 1. Oeq), 4-methoxylin 12.32 g (0. lOOmol, 1. Oeq) And stirred at room temperature for 24 hours. Next, the solvent was distilled off under reduced pressure to obtain Compound g quantitatively. ¾- NMR measurement results are shown below.

Compound g 'H-NMRCCDCl, 300MHz, 35 ° C): δ 3.84 (s, 3H, — OCH), 6.

3 3

93-7.35 (m, 4H, H ^Ph ), 7.37 (dd, J = 7. 7, 4.8Hz, 1H, H), 7.82 (ddd, J b

= 7. 7, 7. 7, 1.6Hz, 1H, H), 8. 21 (dd, J = 7. 7, 1. 6Hz, 1H, H), 8.63 (c d

s, 1H, H), 8.70 (d, J = 4. 8, 1H, H).

e a

[Chemical 52]

-N N— (v / -OMe

Compound g

[0129] (ii) Synthesis of Compound h

[Chemical 53]

(«Ϊ (CH ₂ 0) _n (ii) HCI / = \ ^C!

N— ^ OMe reflux in toluene in 1,4-dioxane ~ ^^ ~ ^ ^ -O e Compound _g Yield: 94.4% Compound h

[0130] In a Schlenk tube under an argon atmosphere, 1.06 g (50. Ommol) of compound, 0.197 g (60. Ommol) of granular paraformaldehyde ((CH 2 O)), and 60 ml of toluene were added.

2 n

The mixture was stirred with heating at ° C for 3 hours. Stir with heating until (CH 2 O) is completely dissolved in toluene.

2 n

. When (CHO) is completely dissolved in toluene, HC1 (4M, 1, 4-dioxane solution) 1. 3

2 n 8 ml (55. Ommol) was added and stirred at room temperature for 2 days. A yellow solid started to precipitate from the moment the HC1 solution was prepared.

The solvent was distilled off under reduced pressure to obtain 12.31 g (94.4%) of a crude product as a yellow solid. This was recrystallized to obtain pure compound h. — NMR and mass spectrometry (MS) measurement results are shown below.

Compound h 'H-NMRCCDCl, 300MHz, 35 ° C): δ 3.88 (s, 3H, — OCH), 7

3 3

.03-7.76 (m, 4H, H ^Ph ), 7.22— 9.42 (4H, H), 7.88 (s, 1H, H), 12 b, c, d, ef

.02 (s, 1H, H).

a

MS (FAB ⁺ ): m / z = 224.8 (M +)

[Chemical 54]

Compound 3

[(COD) IrCl] 70 mg (0.1 Ommol), NaOMe 58 mg (l.

2

lOmmol), degassed 2-Ethoxyethanol (45 ml) was placed in a Schlenk and stirred for 2.5 hours at room temperature. It was.

After evaporating the solvent under reduced pressure, column chromatography using degassed solvent (CH C1) 'silica gel

twenty two

Purification was performed with GRAPHI. 51 mg (0.059 mmol, yield 28%) of a yellow solid product (Compound 3) was obtained. Identification was carried out by ¹ H-NMR (solvent: deuterium form, see Fig. 10). The measurement results of EI-MS are shown below. MS (EI ⁺ ): m / z = 862.1 (M +)

Example 6 (Synthesis of Transition Metal Complex Compound 4)

Compound 4 was synthesized by the following reaction process.

(i) Synthesis of compound i

[Chemical 56]

Compound i

[0134] 100 milliliter flask [this, 2-pyridinecanoleboxylenedehydride (0. 556 milliliter nore, 624. Lmg, 5. 826 mmol, 1. Oeq.), 3-amino-2-methoxydibenzofuran (1 347g, 5.826mmol) and toluene (50ml) and a Dean-Stark trap was attached to remove water. This solution was refluxed at about 130 ° C. overnight. After removing the solvent, an oily product was obtained as a crude product (1.801 g (yield 103.5%)). As a result of purification by column chromatography (developing solvent: ethyl acetate Z-hexane = 1/2), 1.08 g of the target compound i was obtained (yield 61.1%). The measurement results of NMR are shown below.

'H-NMROOOMHz, CDC1, 35 ° C): 6 4. 02 (s, 3H, CH), 7. 35 (m, 2H)

3 3

, 7.39 (ddd, J = l. 0, 2. 4, 7.5 Hz, 1H), 7.45 (dd, J = 0. 9, 7. 6Hz, 1H), 7.48 (s, 1H ), 7.55 (d, J = 8.1, 1H), 7.83 (ddd, J = 0. 9, 1. 7, 7. 9 Hz, 1H), 7.91 (m, 1H), 8. 31 (d, J = 7.9Hz, 1H), 8. 72 (m, 1H), 8. 73 (s, 1 H)

[0135] (ii) Synthesis of Compound j

[Chemical 57]

Compound i Compound j

In a 100 milliliter flask, a mixture i (l. 080 g, 3.57 mmol, 1. Oeq.), 91% noraaldehyde (117. Omg, 3.57 mmol, 1.0 eq.) And toluene ( 50ml) The mixture was stirred at room temperature for 1 day and heated to about 60 ° C for 8 hours to dissolve paraformaldehyde. Thereafter, hydrochloric acid (4M, dioxane solution) (1.25 ml, 6 mmol, 1.7 eq.) Was slowly added dropwise to obtain a reddish brown suspension, which was stirred at room temperature for 14 hours. This suspension was washed with toluene (20 ml XI), THF (20 ml × 3) by a centrifuge to obtain 0.967 g of compound j as a light brown solid (yield 77.2%) -ΝΜ The measurement results of R are shown below.

— NMR (300MHz, DMSO—d, 35 ° C): 64.03 (s, 3H, CH), 7.29 (dt, J

6 3

= 1.2, 6.8, 1H, H ² ), 7.36 (m, t— like, 1H, H ³ ), 7.50 (m, t— like, 1H, H n), 7.63 (m, t— like, 1H, H ¹⁰ ), 7.79 (d, J = 8.3Hz, 1H, H ⁹ ), 7.95 (d, J = 9.2Hz, 1H, H ⁴ ), 8.22 (s, 1H, H ⁸ ), 8.27 (s, 1H, H ⁷ ), 8.31 (d, J = 7.6 Hz, 1H, H ¹² ), 8.61 (s, 1H, H ⁵ ), 8.68 (dd, J = 0.9, 7.0 Hz, 1H, H ¹ ), 10.23 (d — Like, J = l.2Hz, 1H, H ⁶ )

[Chemical 58]

Me

4- 5-. , 8-

9- 10-

■ kN

1. * 6 ^N -A 7- re 12-

[0137] (iii) Synthesis of Compound k

[Chemical 59]

Compound k

[0138] [(COD) IrCl] (49.5mg, 0.0

2

7 mmol, 1 · Oeq.), Solvent ethanol 5 · 0 ml, t-BuOK (tertiary butoxy potassium) (49.6 mg, 0.44 mmol, 6. Oeq.) Were added and stirred for 30 months at room temperature. Next, compound j (103.4 mg, 0.29 mmol, 4. Oeq) was added and stirred at room temperature. Next, the solvent was distilled off under reduced pressure to obtain a solid residue. Thin-layer chromatography of the solid using methanol ZCH CI = iZio as the solvent

twenty two

To obtain 51.6 mg of compound k as a red-orange solid (yield 36.3%). The measurement results of ¹³ C NMR and FAB-MS are shown below.

NMR (300MHz, CDC1, 35 ° C): δ 1.50—1.65 (m, 2H, H), 1.93

3 COD

-2.04 (m, 2H, H), 2.35 (m, 4H, H), 3.38 (m, 2H, H), 3.76 (

COD COD COD

s, 3H, Me), 4.69-4.74 (m, 2H, H), 5.38 (dt, J = l.2, 6.9Hz, 2H)

COD

, 6.39 (dd, J = 6.5, 9.2Hz, 2H), 7.00 (s, 2H), 7.37— 7.50 (m, 10H), 7.58 (s, 2H), 7.59 (s, 2H), 8.05 (td, J = 1.0, 7.6Hz, 2H)

1 ³ C-NMR (75 MHz, CDC1, 35 ° C): δ 27.11, 35.91, 56.59, 72.83, 81.

Three

54, 102.90, 111.02, 111.89, 112.09, 114.94, 118.07, 121.27, 122. 19, 123.35, 123.48, 126.44, 126.79, 128.28, 130.64, 148.66, 1 50.24, 157.08, 168.99. (PS: Lack of one ¹³ C signal )

FAB-MS: m / z = 829.1 ([M] + — CI)

[0139] (iv) Synthesis of Compound 1 (or Compound 1 ')

[Chemical 60]

Compound k Compound Compound

[0140] The Schlenk tube of 30 milliliters was charged with the compound k (50. Omg, 0 · 052 mmol) and 2 ethoxyethanol (5 milliliters) and refluxed for 2 hours. The solution became a red-orange to yellow suspension. Discolored to liquid. The solvent was removed under reduced pressure, and the resulting solid was replaced with CH C1 (3 ml), M

twenty two

eOH (3 ^ UU ^ h / V), EtOH (3 ^ UU ^ h / V), THF (3 ^ U y ^ h / V) ¾tJ ^ CH CNO ^ UU

Three

The compound 1 or compound 1 ′ was obtained as a light yellow solid (44.3 mg, yield 82.2%). — NMR measurement results are shown below.

— NMR (300MHz, DMSO d, 35 ° C): δ 3.89 (d, J = l.4 Hz, 12H, Me

6

), 6.47 (dd, J = 7.9, 33.8Hz, 4H), 6.72 (dd, J = 7.1, 14.3Hz, 4H), 7 04- 7. 25 (m, 12H), 7. 34 (s, 4H), 7. 79— 7. 93 (m, 8H), 8. 99 (d, J = 9.2 Hz, 4H), 9 79 (dd, J = 7. 1, 22. 6Hz, 4H).

FAB-MS: m / z 819. There was no parent peak at mZz = 1708.3 in FAB—MS.

[Chemical 61]

Molecular weight 1708.3 Molecular weight 819

(v) Synthesis of transition metal complex (compound 4)

[Chemical 62]

Compound I Compound I 'Compound 4

mer.body

[0142] Compound 1 or Compound (74.3 mg, 0.087 mmol, 1. Oeq.), Compound j (33.6 mg, 0.096 mmol, 1) was placed in a 30 ml Schlenk tube under an argon stream. leq), Ag O

2

(120. 9 mg, 0.522 mmol, 6. Oeq) and 2-ethoxyethanolanol (8 midi-zole) were collected and refluxed at 135 ° C for 24 hours while protected from light with aluminum foil. The resulting tan suspension precipitated with the silver salt on the tube surface. Use CH C1 as the solvent and filter with Celite Z silica gel.

twenty two

Purification was performed by rush column chromatography to obtain compound 4 (mer. Form, 73.4 mg, yield 74.5%) as a light yellow solid. The analysis results of Compound 4 are shown below.

[0143] FD—MS of compound 4: The maximum peak value was 1132, which was in agreement with the calculated value (calculated value M + molecule ion peak> = 1132).

The measurement conditions of FD-MS measurement (field desorption ion mass spectrometry) were as follows. Device: HX110 (manufactured by JEOL Ltd.)

Condition: Acceleration voltage 8kV

Scan range mZz = 50 to 1500

Emitter type carbon

Emitter current 0mA → 2mAZ min → 40mA (10 min hold)

The ¹ H- NMR of Compound 4 shown in FIG. 11.

Cyclic voltammetry was measured under the following conditions.

Device: HV; 5—100 electrochemical instruments (HoKuto DenKo corp.), LOOmVZs scan rate of 0.001M compound 4 and 0.1M TBAPF [hexa

6 Fluorophosphate Tetrabutyl Ammonium] (in CH C1) solution.

twenty two

Reference electrode: Carbon electrode

Counter electrode: Pt

Reference electrode: AgZAgNO

Three

E ^Redl (irr) = — 1. 52V (or— 1. 2 IV), E ° ^xl (irr) = 0. 27 V, E ° ^x2 (irr) = 0. 75V Cyclic voltammetry measurement of compound 4 Figure 12 shows.

The emission spectrum of compound 4 at room temperature is shown in FIG. 13 (solvent: methylene chloride).

The emission spectrum of Compound 4 at 77K is shown in FIG. 14 (solvent: methylene chloride).

Industrial applicability

As described above in detail, the transition metal complex compound having a metal carbene bond of the present invention has an electroluminescence property, has high luminous efficiency, and can provide an organic EL device. Moreover, according to the method for producing a transition metal complex compound of the present invention, a transition metal complex compound can be produced efficiently.

Claims

The scope of the claims

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

[In the general formula (1), C (carbon atom) → M represents a metal carbene bond, a bond indicated by a solid line (−) represents a covalent bond, and a bond indicated by an arrow (→) represents a coordinate bond. . M represents a metal atom of iridium (Ir), platinum (Pt), rhodium (Rh) or palladium (Pd). L ¹ and L ² each independently represent a monodentate ligand or a bridged bidentate ligand (L ¹ -L ² ) in which L ¹ and L ² are bridged. k is an integer from 1 to 3, i is an integer from 0 to 2, and k + i represents the valence of metal M. j represents an integer of 0 to 4. When there are a plurality of i and j, L ¹ and L ² may be the same or different, and adjacent ones may be bridged together.

L ² is a heterocyclic ring having 3 to 30 nuclear atoms that may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms that may have a substituent, a carboxylic acid amide having 1 to 30 carbon atoms, May have a substituent, phosphine which may have a substituent, iso-tolyl which may have a substituent, an ether having 1 to 30 carbon atoms. , You may have a substituent! A thioether or a substituent containing a double bond-containing compound having 1 to 30 carbon atoms, and when L ¹ and L ² are cross-linked, Is a valent group.

R ¹ and R ² each independently have a hydrogen atom, a halogen atom, a thiociano group, a cyano group, a nitro group, —S (= 0) R ¹⁸ group, —S (= 0) R ¹⁸ , and a substituent. 1 to 30 carbon atoms

2

An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituent. Moly! Cycloalkyl group having 3 to 30 carbon atoms, aralkyl group having 7 to 40 carbon atoms which may have a substituent, and optionally having a alkenyl group having 2 to 30 carbon atoms A heterocyclic group having 3 to 30 heteronuclear atoms, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, and a substituent. An arylamino group having 6 to 30 nuclear carbon atoms or a substituent, an alkylamino group having 3 to 30 nuclear atoms, an arylamino group having 6 to 30 carbon atoms which may have a substituent, or a substituent An alkylsilyl group having 3 to 30 nucleus atoms, may have a substituent !, an arylsilylsilyl group having 6 to 30 carbon atoms, a carboxyl-containing group having 1 to 30 carbon atoms, and Z ³ When CR ^2, R ¹ and R ² may be crosslinked.

(R ¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, a substituted group. May have an aromatic hydrocarbon group having 6 to 30 carbon atoms, may have a substituent! May have a cycloalkyl group having 3 to 50 carbon atoms, or a substituent. It may have a aralkyl group having 7 to 40 carbon atoms, a substituent, a alkenyl group having 2 to 30 carbon atoms, or a substituent, a heterocyclic group having 3 to 30 nuclear atoms, An optionally substituted alkoxy group having 1 to 30 carbon atoms, which may have a substituent, an aryloxy group having 6 to 30 nuclear carbon atoms, or a substituent, which has 3 to 30 carbon atoms An alkylamino group, an arylamino group having 6 to 30 carbon atoms which may have a substituent, and a substituent. It may have an alkylsilyl group having 3 to 30 carbon atoms, a substituent, an arylsilylsilyl group having 6 to 30 carbon atoms, or a substituent, and a carboxyl group having 1 to 30 carbon atoms. It is a contained group. )

When k is more than one,

2. The transition metal complex compound having a metal carbene bond according to claim 1, wherein M is Ir.

[3] The transition metal complex compound having a metal carbene bond according to claim 1, represented by the following general formula (2).

[Chemical 2]

[In the general formula (2), C (carbon atom) → M represents a metal carbene bond.

M and k are the same as described above, m is an integer of 0 to 2, and k + m represents the valence of the metal M.

R ^{3 to} R ¹⁷ are each independently a hydrogen atom, a halogen atom, a thiociano group, a cyano group, a nitro group, —S (= 0) R ¹⁸ group, —S (= 0) R ¹⁸ [R ¹⁸ is Same], may have a substituent

2

V, an alkyl group having 1 to 30 carbon atoms, a substituent, a halogenated alkyl group having 1 to 30 carbon atoms, and an aromatic carbon atom having 6 to 30 nuclear carbon atoms that may have a substituent It may have a hydrogen group, a substituent, a cycloalkyl group having 3 to 30 nuclear carbon atoms, a substituent, a aralkyl group having 7 to 40 carbon atoms, or an optionally substituted carbon. It may have a alkenyl group having 2 to 30 carbon atoms, a substituent, a heterocyclic group having 3 to 30 nuclear atoms, or a substituent, 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 nuclear atoms, an alkylamino group having 3 to 30 nuclear atoms, or a substituent. ~ 30 A reelamino group, an alkylsilyl group having 3 to 30 nuclear atoms which may have a substituent, an arylylsilyl group having 6 to 30 carbon atoms which may have a substituent, and a carboxyl-containing group having 1 to 30 carbon atoms. Yes, R ^{3 to} R ¹⁷ may be adjacent and cross-linked. ]

4. The transition metal complex compound having a metal carbene bond according to claim 3, wherein M is Ir.

[5] A transition metal complex compound having a metal carbene bond represented by the following general formula (3):

[Chemical 3]

[In general formula (3), C (carbon atom) → M represents a metal carbene bond, and the bond indicated by an arrow (→) represents a coordinate bond. M represents a metal atom of iridium (Ir), platinum (Pt), rhodium (Rh) or palladium (Pd). L ² represents a monodentate ligand. j represents an integer of 0-4. When j is plural, each L ² may be the same or different and may be cross-linked.

L ² is a heterocyclic ring having 3 to 30 nuclear atoms that may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms that may have a substituent, a carboxylic acid amide having 1 to 30 carbon atoms, May have a substituent, phosphine which may have a substituent, iso-tolyl which may have a substituent, an ether having 1 to 30 carbon atoms. A thioether having 1 to 30 carbon atoms, or a double bond-containing compound having 1 to 30 carbon atoms which may have a substituent.

L ³ is a conjugate of super strong acids, carboxylic acids, aldehydes, ketones, alcohols, thioalcohols, phenols, amines, amides, aromatics or alkanes with a pKa value of -10 or less. Base, hydrogen ion, halide ion. Z ¹ is a carbon, silicon, nitrogen or phosphorus atom, Z ² is an atom which forms a covalent bond with the substituent R ¹ and is a carbon, silicon, nitrogen or phosphorus atom, and Z ¹ and Z Ring A containing ² and Ring B may have a substituent, an aromatic hydrocarbon group having 3 to 40 nuclear carbon atoms, or a heterocyclic ring having 3 to 40 nuclear atoms that may have a substituent. Z ³ represents a nitrogen atom or CR ^2, and when CR ² is plural, the plural R ² may be the same or different! /.

2

(R ¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, a substituted group. May have an aromatic hydrocarbon group having 6 to 30 carbon atoms, may have a substituent! May have a cycloalkyl group having 3 to 50 carbon atoms, or a substituent. It may have a aralkyl group having 7 to 40 carbon atoms, a substituent, a alkenyl group having 2 to 30 carbon atoms, or a substituent, a heterocyclic group having 3 to 30 nuclear atoms, An optionally substituted alkoxy group having 1 to 30 carbon atoms, which may have a substituent, an aryloxy group having 6 to 30 nuclear carbon atoms, or a substituent, which has 3 to 30 carbon atoms An alkylamino group, a C6-C30 arylamino group which may have a substituent, a substituent, a C3-C30 alkylsilyl group, or a substituent; Carbon number 6 30 Arirushiriru group, which may have a substituent Yo, Ru carboxyl-containing groups der 1 to 30 carbon atoms.) Two ZZZRA rings and two B rings, each of which is the same or different, may be bridged by adjacent ones. ]

The transition metal complex compound having a metal carbene bond represented by the following general formula (4) according to claim 5, wherein M is Ir.

[Chemical 4]

[In the general formula (4), C (carbon atom) → M represents a metal carbene bond, a bond indicated by a solid line (-) indicates a covalent bond, and a bond indicated by an arrow (→) indicates a coordinate bond. . M represents a metal atom of iridium (Ir), platinum (Pt), rhodium (Rh) or palladium (Pd). L ² represents a monodentate ligand. j represents an integer of 0 to 4. When j is plural, each L ² may be the same or different and may be cross-linked.

L ² is a heterocyclic ring having 3 to 30 nuclear atoms that may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms that may have a substituent, a carboxylic acid amide having 1 to 30 carbon atoms, May have a substituent, phosphine which may have a substituent, iso-tolyl which may have a substituent, an ether having 1 to 30 carbon atoms. A ligand comprising a thioether having 1 to 30 carbon atoms, or a double bond-containing compound having 1 to 30 carbon atoms, and L ¹ When L ² is crosslinked, it is a monovalent group of each ligand.

L ³ is a super strong acid, carboxylic acid, aldehyde, ketone, alcohol, thioalcohol, phenol, amine, amide or aromatic with a pKa value of -10 or less

, An alkane conjugate base, or a hydrogen ion or halide ion.

Z ¹ is an atom that forms a covalent bond with metal M and is a carbon, silicon, nitrogen, or phosphorus atom. Z ² is an atom that forms a covalent bond with the substituent R ¹ and is a carbon, silicon, nitrogen, or phosphorus atom, and the A ring and the B ring containing Z ¹ and Z ² have a substituent. An aromatic hydrocarbon group having 3 to 40 nuclear carbon atoms or a heterocyclic group having 3 to 40 nuclear atoms which may have a substituent, Z ³ represents a nitrogen atom or CR ² ; When there are a plurality of CR ² , the plurality of R ² may be the same or different.

R ¹ and R ² each independently have a hydrogen atom, a halogen atom, a thiociano group, a cyano group, a nitro group, —S (= 0) ² R ¹⁸ group, —S (= 0) R ¹⁸ , and a substituent. C 1 -C 30 alkyl group, C 1 -C 30 halogenoalkyl group which may have a substituent, and C 6 -C 30 aromatic fragrance May have an aromatic hydrocarbon group or a substituent! A cycloalkyl group having 3 to 30 carbon atoms, a aralkyl group having 7 to 40 carbon atoms that may have a substituent, or a substituent. It may have a C2-C30 alkenyl group and a substituent! Heterocyclic group having 3 to 30 carbon atoms, a C1-C30 alkoxy which may have a substituent May have a group, a substituent, an aryloxy group having 6-30 nuclear carbon atoms, a substituent, an alkylamino group having 3-30 nuclear atoms, or an optionally substituted carbon. Number 6-30 It may have a group, a substituent, an alkylsilyl group having 3 to 30 nucleus atoms, or a substituent !, an arylsilylsilyl group having 6 to 30 carbon atoms, and a carboxyl group having 1 to 30 carbon atoms When Z ³ is CR ² , R ¹ and R ² may be cross-linked.

[8] The transition metal complex compound having a metal carbene bond according to claim 7, wherein the M force is r. The iridium compound represented by the following general formula (5) and the imidazo represented by the following general formula (6) A method for producing a transition metal compound having a metal carbene bond, which comprises reacting a lithium salt in the presence of a solvent and a base to produce a transition metal compound represented by the general formula (7).

[Chemical 5]

[In general formulas (5-7), C (carbon atom) → Ir (iridium) represents a metal carbene bond, the bond indicated by a solid line (one) is a covalent bond, and the bond indicated by an arrow (→) is It means coordination bond. L ² represents a monodentate ligand. j represents an integer of 0 to 4. When j is plural, each L ² may be the same or different and may be cross-linked.

L ² is a heterocyclic ring having 3 to 30 nuclear atoms that may have a substituent, a carboxylic acid ester having 1 to 30 carbon atoms that may have a substituent, a carboxylic acid amide having 1 to 30 carbon atoms, May have a substituent, phosphine which may have a substituent, iso-tolyl which may have a substituent, an ether having 1 to 30 carbon atoms. A thioether having 1 to 30 carbon atoms or a compound having a double bond having 1 to 30 carbon atoms When L ¹ and L ² are crosslinked, they are monovalent groups of the above ligands. L ³ is a super strong acid, carboxylic acid, aldehyde, ketone, alcohol, thioalcohol, phenol, amine, amide or aromatic with a pKa value of -10 or less

Represents a conjugate base of alkane, a hydrogen ion, or a halide ion.

Z ¹ is an atom that forms a covalent bond with the metal Ir, and is a carbon, silicon, nitrogen, or phosphorus atom.Z ² is an atom that forms a covalent bond with the substituent R ^1, and is a carbon, silicon, or nitrogen atom. Or ring A, ring A containing Z ¹ and Z ² , and ring B may have a C 3-40 aromatic hydrocarbon group or substituent which may have a substituent. It is a good heterocyclic group having 3 to 40 nuclear atoms, Z ³ represents a nitrogen atom or CR ^2, and when CR ² is plural, plural R ² may be the same or different.

(R ¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may have a substituent, a substituted group. May have an aromatic hydrocarbon group having 6 to 30 carbon atoms, may have a substituent! May have a cycloalkyl group having 3 to 50 carbon atoms, or a substituent. It may have a aralkyl group having 7 to 40 carbon atoms, a substituent, a alkenyl group having 2 to 30 carbon atoms, or a substituent, a heterocyclic group having 3 to 30 nuclear atoms, C1-C30 alkoxy group which may have a substituent, having a substituent However, it may have an aryloxy group having 6-30 nuclear carbon atoms, a substituent, an alkylamino group having 3-30 carbon atoms, an arylamino group having 6-30 carbon atoms which may have a substituent, It may have a substituent, may have an alkylsilyl group having 3 to 30 carbon atoms, may have a substituent, may have an arylylsilyl group having 6 to 30 carbon atoms, or may have a substituent, may have 1 to 30 carboxyl-containing groups. )

10. The method for producing a transition metal compound having a metal carbene bond according to claim 9, wherein the solvent is a tetrahydrofuran derivative.

[11] In an organic electoluminescence 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, the organic thin film layer has at least one layer strength. Or an organic electroluminescent device containing the transition metal complex compound having a metal carbene bond according to 7.

12. The organic electroluminescence device according to claim 11, wherein the light emitting layer contains the transition metal complex compound having a metal carbene bond according to claim 1, 5 or 7 as a light emitting material.

[13] The organic electroluminescent device according to claim 11, wherein the light-emitting layer contains the transition metal complex compound having a metal carbene bond according to claim 1, 5 or 7 as a dopant.

[14] An electron injection layer and a Z or electron transport layer are provided between the light emitting layer and the cathode, and the electron injection layer and the Z or electron transport layer are mainly composed of a π electron deficient nitrogen-containing heterocyclic derivative. The organic electoluminescence device according to claim 11, which is contained as follows.

15. The organic electoluminescence device according to claim 11, wherein a reducing dopant is added to an interface region between the cathode and the organic thin film layer.