CN101253185A - Transition metal coordination compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention provides an organic electroluminescent element with high luminous efficiency and emitting cyan light and a transition metal coordination compound used to obtain the organic electroluminescent element. The transition metal coordination compound has a specific structure including a cross-linked structure. , the organic electroluminescent element holds an organic thin film layer composed of one or more layers having at least a light-emitting layer between a pair of electrodes, wherein at least one layer of the organic thin film layer contains the transition metal coordination compound .

Description

Transition metal coordination compound and organic electroluminescent device using the same

technical field

The present invention relates to a transition metal coordination compound and an organic electroluminescent element using the compound, in particular to an organic electroluminescent element with high luminous efficiency and cyan light emission and a novel transition metal for realizing the organic electroluminescent element coordination compound.

Background technique

An organic electroluminescent element (EL) is a self-luminous element utilizing the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. C.W.Tang et al. from Eastman Kodak reported low-voltage drive organic EL elements based on stacked elements (C.W.Tang, S.A.Vanslyke, Applied Physics Letters, Volume 51, Page 913, 1987, etc.) Since then, research on organic EL elements using organic materials as constituent materials is constantly on the rise. Tang et al. used tris(8-hydroxyquinoline aluminum) in the light-emitting layer, and triphenyldiamine derivatives in the hole-transporting layer. The advantages of the stacked structure include: increasing the injection efficiency of holes into the light-emitting layer; improving the generation efficiency of excitons generated by blocking and recombining electrons injected from the cathode; and trapping excitons generated in the light-emitting layer. As shown in these examples, as an element structure of an organic EL element, a two-layer type of a hole transport (injection) layer and an electron transport light-emitting layer, or a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection) layer are well known. Layered three-layer type. Since the recombination efficiency of injected holes and electrons can be improved in such a multilayer structure device, much effort has been devoted to the device structure and formation method.

As light-emitting materials for organic EL devices, chelate compounds such as tris(8-hydroxyquinoline)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, distyrylarylene derivatives, etc. Luminescent materials such as substances and oxadiazole derivatives are reported to be able to obtain luminescence in the visible region from cyan to red with these substances, and color display devices can be expected to be realized (for example, see Patent Document 1, Patent Document 2, Patent Document 3, etc.) .

In addition, in recent years, it has been proposed to use a phosphorescent material in addition to a fluorescent material in a light emitting layer of an organic EL element (see, for example, Non-Patent Document 1 and Non-Patent Document 2). In this way, the singlet state and the triplet state of the excited state of the phosphorescent material are utilized in the light emitting layer of the organic EL element, thereby achieving high luminous efficiency. When electrons and holes recombine in an organic EL element, due to the difference in spin multiplicity, it is believed that singlet excitons and triplet excitons are generated at a ratio of 1:3. Compared with elements using fluorescence, it can achieve 3 to 4 times the luminous efficiency.

In such an organic EL element, in order not to cause extinction of the excited state of the triplet state or the excitons of the triplet state, conventionally, an anode, a hole transport layer, an organic light-emitting layer, and an electron transport layer (hole blocking layer) are sequentially stacked. ), an electron transport layer, a cathode, and a host compound and a phosphorescent compound for the organic light-emitting layer (for example, refer to Patent Document 4 and Patent Document 5). These patent documents are technologies related to phosphorescent materials that emit red to green light. Furthermore, technologies related to light-emitting materials having cyan-based light-emitting colors are also disclosed (for example, see Patent Document 6, Patent Document 7, Patent Document 8, etc.). However, the lifetime of these devices is very short, and in particular, Patent Documents 7 and 8 describe ligand skeletons in which metals and phosphorus atoms are bonded. Although these luminescent colors are blue, the bond is weak, and heat resistance is remarkably poor. Also, in Patent Document 9, although it is also described about a coordination compound in which an oxygen atom and a nitrogen atom are bonded to a central metal, it does not describe any specific effect of a group bonded to an oxygen atom. In addition, Patent Document 10 discloses a coordination compound in which nitrogen atoms contained in different ring structures are bonded to a central metal. Although the device using this coordination compound exhibits cyan light emission, the external quantum efficiency is as low as 5%. about.

On the other hand, in recent years, studies on transition metal complexes having metal carbene bonds (hereinafter also referred to as carbene complexes) have been conducted (for example, refer to Patent Document 11 and Non-Patent Documents 3 to 11).

Carbene refers to two-coordinated carbon, which is a substance with 2 electrons in the sp ² hybrid orbit and 2p orbit, and the combination of the orbit and spin direction entered by the two electrons can obtain 4 structures, usually Singlet carbene, formed by sp ² hybridized occupied orbitals and 2p empty orbitals.

In the past, carbene coordination compounds were short-lived and unstable, and had been used as reaction intermediates in organic synthesis reactions or synthetic conversion reagents such as addition to olefins. A stable carbene complex and a stable carbene complex formed of a non-aromatic cyclic structure can be further stabilized with nitrogen and phosphorus to obtain a stable acyclic carbene complex. In addition, in recent years, stable carbene complexes have been expected more for catalytic reactions in organic synthesis from the viewpoint of improving catalytic performance by binding them as ligands to transition metals.

In particular, in an olefin metathesis reaction, it has been found that performance is significantly improved by adding or coordinate-stabilizing a carbene complex. In addition, in recent years, studies on the efficiency of the Suzuki coupling reaction, the oxidation of chain alkanes or the selective hydroformylation reaction, or optically active carbene complexes have been carried out. Applications in the field of organic synthesis have attracted attention.

In addition, examples of specific coordination compounds having a carbene iridium bond are listed in the following Non-Patent Document 12 (Tri(carbene)iridium complex formed from a non-heterocyclic carbene ligand) and Non-Patent Document 13 It has been described in (Monocarbene Iridium Complex of Monodentate Coordination Type), but there is no description of its application to the field of organic EL elements and the like.

In addition, Patent Document 11 discloses the synthesis of an iridium coordination compound having a carbene bond, its emission wavelength, and device performance, but the energy efficiency is low, the external quantum efficiency is low, and the emission wavelength is distributed in the ultraviolet region, and the visual efficiency is poor. . Therefore, it is not suitable for light-emitting devices in the visible wavelength region such as organic EL. In addition, due to reasons such as low decomposition temperature and high molecular weight, vacuum vapor deposition cannot be performed. Since the coordination compound is decomposed during vapor deposition, there is a problem of contamination of impurities when making devices.

In addition, Patent Documents 12 to 20 describe complex compounds having various carbene bonds, and disclose cyan light-emitting complex compounds. However, the energy efficiency and the external quantum efficiency are low, and there is no mention of an increase in the lifetime of the luminous lifetime.

On the other hand, Patent Documents ²¹ and 22 disclose that three 2-phenylpyridine -The method of cross-linking at the N, C ² base site, but only discloses a variety with a benzene ring skeleton at the 3-legged cross-linking site, which cannot significantly increase the lifespan, and also does not suggest that it can be used for cyan light emission.

Patent Document 1: JP-A-8-239655

Patent Document 2: Japanese Unexamined Patent Publication No. 7-183561

Patent Document 3: Japanese Unexamined Patent Publication No. 3-200289

Patent Document 4: Specification of US Patent No. 6097147

Patent Document 5: International Publication No. WO01/41512

Patent Document 6: US2001/0025108 Publication

Patent Document 7: US2002/0182441 Publication

Patent Document 8: JP-A-2002-170684

Patent Document 9: JP-A-2003-123982

Patent Document 10: JP-A-2003-133074

Patent Document 11: International Publication No. WO05/019373

Patent document 12: US2005/0258433 publication

Patent Document 13: US2005/0258742 Publication

Patent Document 14: US2005/0260441 Publication

Patent document 15: US2005/0260444 publication

Patent document 16: US2005/0260445 publication

Patent Document 17: US2005/0260446 Publication

Patent Document 18: US2005/0260447 Publication

Patent Document 19: US2005/0260448 Publication

Patent Document 20: US2005/0260449 Gazette

Patent Document 21: US2005/0170206 Publication

Patent Document 22: US2005/0170207 Publication

Non-Patent Document 1: D.F.O Brien and M.A.Baldo et al "Improved energytransferin electrophosphorescent device" Vol.74 No.3, pp442-444, January18, 1999

Non-Patent Document 2: M.A.Baldo et al "Very high-efficiency green organic light-emitting devices based electrophosphorescence" Applied Physics letters Vol.75 No.1, pp4-6, July 5, 1999

Non-Patent Document 3: Chem.Rev.2000, 10, p39

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

Non-Patent Document 5: Angew.Chem.Int.Ed., 2002, 41, p1290

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

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

Non-Patent Document 8: Angew.Chem.Int.Ed., 2002, 41, p1363

Non-Patent Document 9: Angew.Chem.Int.Ed., 2002, 41, p1745

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

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

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

Non-Patent Document 13: Chem.Commun., 2002, p2518

Contents of the invention

The present invention was conceived to solve the above-mentioned problems, and an object of the present invention is to provide an organic EL device that emits cyan light with high luminous efficiency and a novel transition metal complex for realizing it.

As a result of intensive studies to achieve the above object, the present inventors have found that the emission wavelength can be increased by linking (crosslinking) the ligands of the transition metal complex to the transition metal complex. This phenomenon is useful as a technology capable of adjusting the emission wavelength to a predetermined value, and is particularly useful for converting a material having an emission wavelength in the ultraviolet region to a material having an emission wavelength in the cyan region (enlarging the visible wavelength region). They found that by utilizing this technique, an organic EL element that emits blue light with high luminous efficiency can be obtained, and completed the present invention.

That is, the present invention provides a transition metal coordination compound having a ligand having a tridentate or more than a tridentate coordinating tooth formed by a combination of covalent bonds and/or coordinate bonds, and a transition metal complex having And/or the transition metal coordination compound of the ligand of the four-dentate or more than four-dentate coordination teeth formed by the combination of coordination bonds.

In addition, the present invention provides a transition metal complex having a metal carbene bond represented by the following general formula (1) or (6).

[chemical 1]

[In the general formula (1), the bond shown by the solid line (-) represents a covalent bond, the bond represented by an arrow (→) represents a coordination bond, and at least one of L ² →M and L ⁴ →M represents a metallic carbon olefinic bond. M represents a metal atom of iridium (Ir) or platinum (Pt). L ¹ -L ² and L ³ -L ⁴ represent cross-linked bidentate ligands, L ⁵ and L ⁶ each independently represent monodentate ligands or cross-linked bidentate ligands in which L ⁵ and L ⁶ are cross-linked Body (L ⁵ -L ⁶ ), L ¹ and L ³ , L ¹ and L ⁴ , L ² and L 3 , L ² and L ⁴ , L ¹ and L ⁵ , L ¹ and L ⁶ , ^{L 2 and} L ⁵ , L ² and L ⁶ , L ³ and L ⁵ , L ³ and L ⁶ , L ⁴ and L ⁵ and L ⁴ and L ⁶ at least one via the crosslinking group -Z ¹ -(Z ¹ is from aromatic hydrocarbon , heterocyclic groups, chain alkanes, chain alkenes, and their carbon atoms are replaced by any one of silicon atoms, nitrogen atoms, sulfur atoms, oxygen atoms, phosphorus atoms, and boron atoms; or a compound selected from A divalent residue formed by combining these may have a substituent) for crosslinking. When there are a plurality of crosslinking groups -Z ¹ -, each may be the same or different. i represents an integer of 0 to 1, and 2+i represents the atomic valence of the metal M. j represents the integer of 0-4. When i and j are plural, each of L ⁵ and L ⁶ may be the same or different, and adjacent groups may be cross-linked.

^L1 and ^L3 each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, a divalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent, or A divalent carboxyl-containing group having 1 to 30 carbon atoms that has a substituent, a divalent amino or hydroxyl-containing hydrocarbon group that may also have a substituent, and a ring substituent having 3 to 50 ring carbon atoms that may also have a substituent Alkyl group, an optionally substituted C1-30 alkylene group, an optionally substituted C2-30 alkenylene group, an optionally substituted C7-40 aralkylene group base;

L ² and L ⁴ each independently represent a monovalent group having carbene carbon which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may also have a substituent, or a monovalent aromatic hydrocarbon group which may have a substituent A monovalent heterocyclic group having 3 to 30 ring atoms, at least one of L ² and L ⁴ is a monovalent group having carbene carbon which may have a substituent.

^L5 is a monovalent aromatic hydrocarbon group with 6 to 30 ring carbon atoms that may have a substituent, a monovalent heterocyclic group with 3 to 30 ring atoms that may have a substituent, or a carbon number that may have a substituent A monovalent carboxyl group of 1 to 30, a monovalent hydrocarbon group containing an amino group or a hydroxyl group that may have a substituent, a cycloalkyl group with 3 to 50 ring carbon atoms that may have a substituent, and a carbon number that may have a substituent An alkyl group of 1 to 30, an alkenyl group of 2 to 30 carbons which may also have a substituent, an aralkyl group of 7 to 40 carbons which may also have a substituent, and when ^L5 and ^L6 are crosslinked is the divalent group of each group;

^L6 is a heterocyclic group with 3 to 30 ring carbon atoms that may also have a substituent, a carboxylic acid ester with 1 to 30 carbon atoms or a carboxylic acid amide with 1 to 30 carbon atoms that may also have a substituent, and may also have Amines with substituents, phosphines with substituents, isonitriles with substituents, ethers with 1 to 30 carbon atoms with substituents, thioethers with 1 to 30 carbon atoms with substituents , or a double bond-containing compound having 1 to 30 carbon atoms that may also have a substituent, and when L ⁵ and L ⁶ are cross-linked, they are monovalent groups of the respective ligands. ].

[Chem 2]

[In general formula (6), A represents the cross-linked bidentate ligand group formed by L ¹¹ -(Z ¹¹ ) _d -L ¹² , B represents the cross-linked bidentate ligand group formed by L ¹³ -(Z ¹² ) _e -L ¹⁴ In addition, C represents a cross-linked bidentate ligand group formed by L ¹⁵ -(Z ¹³ ) _f -L ¹⁶ . L ¹¹ -, L ¹³ - and L ¹⁵ - represent covalent bonds with Ir (iridium) respectively (L ¹¹ -Ir, L ¹³ -Ir and L ¹⁵ -Ir), L ¹² →, L ¹⁴ → and L ¹⁶ → Each represents a coordination bond with Ir (iridium) (L ¹² →Ir, L ¹⁴ →Ir, and L ¹⁶ →Ir).

^X1 is a cross-linking group formed by an acyclic structure with an atomic number of 1 to 18, and is a crosslinking group selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom. A trivalent residue of a compound composed of atoms may have a substituent.

Y ¹ represents the cross-linking group that combines X and A, Y ² represents the cross-linking group that combines X and B, Y ³ represents the cross-linking group that combines X and C, Y ¹ is combined with L ¹¹ , L ¹² or Z ¹¹ , Y ² binds to L ¹³ , L ¹⁴ or Z ¹² , Y ³ binds to L ¹⁵ , L ¹⁶ or Z ¹³ . Y ¹ , Y ² and Y ³ each independently represent a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, It may also have a substituent. a, b, and c each independently represent an integer of 0 to 10, and when a, b, or c is a plural number, a plurality of Y ¹ , Y ^{2 ,} or Y ³ may be the same or different.

Z ¹¹ represents the cross-linking group combining L ¹¹ and L ¹² , Z ¹² represents the cross-linking group combining L ¹³ and L ¹⁴ , Z ¹³ represents the cross-linking group combining L ¹⁵ and L 16, ^{Z 11 ,} Z ¹² and Z ¹³ Each independently represents a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, and may have a substituent. When Z ¹¹ is directly bonded to Y ¹ , when Z ¹² is directly bonded to Y ² , or when Z ¹³ is directly bonded to Y ³ , Z ¹¹ , Z ¹² and Z ¹³ become corresponding trivalent groups, respectively. d, e, and f each independently represent an integer of 0 to 10, and when d, e, or f is a plural number, a plurality of Z ¹¹ , Z ^{12 ,} or Z ¹³ may be the same or different.

L ¹¹ , L ¹³ and L ¹⁵ each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, or a divalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent , a divalent carboxyl-containing group with 1 to 30 carbon atoms that may also have a substituent, a divalent amino or hydroxyl-containing hydrocarbon group that may also have a substituent, or a ring with 3 to 50 carbon atoms that may also have a substituent cycloalkylene group, an alkylene group with 1 to 30 carbon atoms that may have a substituent, an alkenylene group with 2 to 30 carbon atoms that may also have a substituent, and an alkenylene group with 7 to 40 carbon atoms that may also have a substituent Aralkylene, when L ¹¹ is directly combined with Y ¹ , when L ¹³ is directly combined with Y ² , or when L ¹⁵ is directly combined with Y ³ , L ¹¹ , L ¹³ and L ¹⁵ become the corresponding trivalent group.

L ¹² , L ¹⁴ and L ¹⁶ each independently represent a monovalent group having carbene carbon which may also have a substituent, or a monovalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent, when L When ¹² is directly bonded to ^Y1 , when ^L14 is directly bonded to ^Y2 , or when ^L16 is directly bonded to ^Y3 , ^L12 , ^L14 , and ^L16 become corresponding divalent groups, respectively. ].

In addition, the present invention provides an organic EL element 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 contains the transition metal complexes.

Description of drawings

FIG. 1 is a graph showing the ¹ H-NMR spectrum of metal complex 1 obtained in Example 1. FIG.

2 is a graph showing the ¹ H-NMR spectrum of Comparative Compound 1 obtained in Comparative Example 1. FIG.

3 is a graph showing the ¹ H-NMR spectrum of Comparative Compound 2 obtained in Comparative Example 2. FIG.

FIG. 4 is a graph showing the emission spectra of metal complex 1, comparative compound 1, and comparative compound 2. FIG.

Detailed ways

The present invention is a transition metal coordination compound having a ligand containing a tridentate or more than a tridentate coordination tooth formed by a combination of covalent bonds and/or coordination bonds, and a transition metal coordination compound containing A transition metal coordination compound of a ligand of a four-dentate or more than four-dentate coordination tooth formed by a combination of bonds. Preferably, the transition metal complex has a metal-carbon olefin bond, and the metal of the transition metal complex is preferably iridium.

Examples of such transition metal complexes include transition metal complexes having a metal-carbene bond represented by the following general formula (1) or (6).

[Chem 3]

In the general formula (1), the bond shown by the solid line (-) represents a covalent bond, the bond represented by an arrow (→) represents a coordination bond, and at least one of L ² →M and L ⁴ →M represents a metallocarbene key.

In the general formula (1), M represents a metal atom of iridium (Ir) or platinum (Pt). Ir is preferred.

In general formula (1), L ¹ →L ² and L ³ →L ⁴ represent cross-linked bidentate ligands, L ⁵ and L ⁶ each independently represent monodentate ligands or L ⁵ and L ⁶ are cross-linked Linked cross-linked bidentate ligands (L ⁵ -L ⁶ ). In addition, L ¹ and L ³ , L ¹ and L ⁴ , L ² and L ³ , L ² and L ⁴ , L ¹ and L ⁵ , L 1 and L ⁶ , L ² and L ⁵ , ^{L 2 and} L ⁶ , At least one of L ³ and L ⁵ , L ³ and L ⁶ , L ⁴ and L ⁵ , and L ⁴ and L ⁶ is cross-linked via a cross-linking group -Z ¹ -. i represents an integer of 0 to 1, and 2+i represents the atomic valence of the metal M. j represents the integer of 0-4. When i and j are plural, each of L ⁵ and L ⁶ may be the same or different, and adjacent groups may be cross-linked.

^Z1 is from aromatic hydrocarbons, heterocyclic groups, chain alkanes, chain alkenes, and compounds whose carbon atoms are substituted by any of silicon atoms, nitrogen atoms, sulfur atoms, oxygen atoms, phosphorus atoms, and boron atoms The selected compound; or the divalent residue formed by their combination may have a substituent. When there are a plurality of crosslinking groups -Z ¹ -, each may be the same or different.

Specific examples of ^Z1 include an α,ω-alkylene crosslinking group having 1 to 20 carbons, an α,ω-alkylene crosslinking group having an ether bond having 1 to 20 carbons, a carbon number 1-20 α, ω-alkylene cross-linking groups with thioether bonds, α, ω-alkylene cross-linking groups with 1-20 carbon-silicon bonds, 1-20 carbons with carbon α, ω-alkylene cross-linking group with nitrogen bond, α, ω-alkylene cross-linking group with carbon number 1-20 with carbon-phosphorus bond, α with carbon-carbon double bond with 1-20, ω-alkylene crosslinking group, α,ω-alkylene crosslinking group with 1 to 20 carbons having a carbon-carbon triple bond, α,ω-alkylene with 1 to 20 carbons having an arylene group The crosslinking group, the α,ω-alkylene crosslinking group having a heterocyclic group having 1 to 20 ring atoms, and the like are preferably compounds composed of only carbon atoms and hydrogen atoms among the above.

When there are multiple substituents for ^Z1 above, each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 30 carbon atoms which may also have a substituent. A haloalkyl group of 30, an aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, a cycloalkyl group having 3 to 30 ring carbon atoms which may also have a substituent, and a carbon number 7 which may also have a substituent An aralkyl group with ∼40 carbon atoms, an alkenyl group with 2 to 30 carbon atoms which may also have a substituent, a heterocyclic group with 3 to 30 ring atoms which may also have a substituent, a carbon atom group with 1 to 30 carbon atoms which may also have a substituent An alkoxy group of 30, an aryloxy group having 6 to 30 ring carbon atoms which may have a substituent, an alkylamino group having 3 to 30 ring atoms which may also have a substituent, and an optionally substituted aryloxy group having 3 to 30 ring atoms An alkylsilyl group with ∼30 carbon atoms, an arylsilyl group with 6 to 30 carbon atoms which may have a substituent, and a carboxyl group-containing group with 1 to 30 carbon atoms, but are not limited thereto. Specific examples of each of these groups are the same as described below. Among the above, compounds composed of only halogen atoms, or carbon atoms and hydrogen atoms are preferred.

Specific examples of ^Z1 include the structures described below (* indicates the position of a bond, for example, the following (a) indicates a 1,2-ethylene bridge).

[chemical 4]

In the general formula (1), L ¹ and L ³ each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 3 to 30 ring atoms which may also have a substituent. A valent heterocyclic group, a divalent carboxyl-containing group having 1 to 30 carbon atoms that may have a substituent, a divalent amino- or hydroxyl-containing hydrocarbon group that may also have a substituent, or a ring carbon atom that may also have a substituent A cycloalkylene group having 3 to 50 carbon atoms, an alkylene group having 1 to 30 carbon atoms that may have a substituent, an alkenylene group having 2 to 30 carbon atoms that may also have a substituent, a carbon number that may have a substituent 7-40 aralkylene.

In the general formula (1), L ² and L ⁴ each independently represent a monovalent group having carbene carbon which may have a substituent, or a monovalent aromatic group having 6 to 30 ring carbon atoms which may also have a substituent. A hydrocarbon group, a monovalent heterocyclic group having 3 to 30 ring atoms which may have a substituent, at least one of L ² and L ⁴ is a monovalent group having carbene carbon which may also have a substituent.

In the general formula (1), L is ^{a monovalent} aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, a monovalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent, or A monovalent carboxyl group having 1 to 30 carbon atoms which may have a substituent, a monovalent hydrocarbon group containing an amino group or a hydroxyl group which may also have a substituent, a cycloalkyl group having 3 to 50 ring carbon atoms which may also have a substituent, An alkyl group having 1 to 30 carbons which may have a substituent, an alkenyl group having 2 to 30 carbons which may also have a substituent, an aralkyl group having 7 to 40 carbons which may also have a substituent, and when L ⁵ and L ⁶ are divalent groups of the respective groups when they are cross-linked.

Specific examples of each group represented by L ¹ to L ⁵ will be described below.

基、全氟代苯基等，以及使它们变为2价基团后的基团。The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 18 ring carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, and 9-anthracenyl , 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthalenyl, 2-naphthalenyl, 9-naphthalenyl, 1-pyrene Base, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-triphenyl-4-yl, p-triphenyl-3-yl, p-triphenyl- 2-yl, m-triphenyl-4-yl, m-triphenyl-3-yl, m-triphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-anthracenyl, 4'-methylbiphenyl , 4"-tert-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylylene, 3,4-xylylene, 2 , 5-xylylene,

group, perfluorophenyl group, etc., and the group after making them divalent groups.

Among them, phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-tolyl, 3,4-xylylene groups, etc., and the groups after making them into divalent groups.

The heterocyclic group is preferably a heterocyclic group having 3 to 18 ring atoms, for example, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridyl, 1 -imidazolyl, 2-imidazolyl, 1-pyrazolyl, 1-indoxazinyl, 2-indoxazinyl, 3-indoxazinyl, 5-indoxazinyl, 6-indoxazinyl, 7-indoxazinyl, 8-indoxazinyl, 2-imidazopyridyl, 3-imidazopyridyl, 5-imidazopyridyl, 6-imidazopyridyl, 7-imidazopyridyl, 8 -imidazopyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl Base, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuran Base, 7-benzofuryl, 1-isobenzofuryl, 3-isobenzofuryl, 4-isobenzofuryl, 5-isobenzofuryl, 6-isobenzofuryl, 7 -isobenzofuryl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1 -isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 8-isoquinolinyl, 2- Quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, β -carboline-1-yl, β-carboline-3-yl, β-carboline-4-yl, β-carboline-5-yl, β-carboline-6-yl, β-carboline-7 -yl, β-carboline-8-yl, β-carboline-9-yl, 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl , 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9 -Acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5 - Base, 1,7-phenanthroline-6-yl, 1,7-phenanthroline-8-yl, 1,7-phenanthroline-9-yl, 1,7-phenanthroline-10-yl , 1,8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl, 1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl, 1 , 8-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl, 1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl, 1,9 -Phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-yl, 1,9-phenanthroline Phenanthroline-6-yl, 1,9-phenanthroline-7-yl, 1,9-phenanthroline-8-yl, 1,9-phenanthroline-10-yl, 1,10-phenanthroline -2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 2,9-phenanthroline-1 - Base, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline-5-yl, 2,9-phenanthroline-6-yl , 2,9-phenanthrolin-7-yl, 2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl, 2,8-phenanthrolin-1-yl, 2 , 8-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl, 2,8-phenanthrolin-6-yl, 2,8 -Phenanthroline-7-yl, 2,8-phenanthroline-9-yl, 2,8-phenanthroline-10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline Phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-yl, 2,7-phenanthroline-6-yl, 2,7-phenanthroline -8-yl, 2,7-phenanthrolin-9-yl, 2,7-phenanthrolin-10-yl, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2- Phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phen Oxazinyl, 10-phenoxazinyl, 2-oxazolinyl, 4-oxazolinyl, 5-oxazolinyl, 2-oxadiazolinyl, 5-oxadiazolinyl, 3- Furazanyl, 2-thianthyl, 3-thianthyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl, 2-methyl Pyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl, 2-tert-butyl Basepyrrol-4-yl, 3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl- 3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indolyl, 4-tert-butyl-1-indolyl, 2-tert-butyl-3-indolyl Indolyl, 4-tert-butyl-3-indolyl, pyrrolidine, pyrazolidine, piperazine, etc., and groups made of these divalent groups.

Among them, 2-pyridyl, 1-indole azinyl, 2-indole azinyl, 3-indole azinyl, 5-indole azinyl, 6-indole azinyl, 7-indole azinyl, 8 -indoxazinyl, 2-imidazopyridyl, 3-imidazopyridyl, 5-imidazopyridyl, 6-imidazopyridyl, 7-imidazopyridyl, 8-imidazopyridyl, 3- Pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 1 - carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, and their divalent groups.

Examples of the carboxyl group-containing group include ester bonds (-C(=O)O-), methyl esters, ethyl esters, butyl esters, and groups obtained by making them divalent groups.

Examples of the cycloalkyl group and cycloalkylene group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 1-adamantyl, 2-adamantyl , 1-norbornyl group, 2-norbornyl group, etc., and groups obtained by making them divalent groups.

As the above-mentioned alkyl group and alkylene group, a group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group , tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-decyl, n-dodecyl, n-tridecyl, n- Tetradecyl, n-pentadecanyl, n-hexadecanyl, n-heptadecanyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl Base, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl base, 1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxytert-butyl, 1,2,3-trihydroxypropyl, aminomethyl, 1-aminoethyl Base, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl, 2,3-diaminotert-butyl, 1,2,3- Triaminopropyl, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl, 1,3-dicyanoisobutyl Propyl, 2,3-dicyano-tert-butyl, 1,2,3-tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 1,2-di Nitroethyl, 2,3-dinitro-tert-butyl, 1,2,3-trinitropropyl, cyclopentyl, cyclohexyl, cyclooctyl, 3,5-tetramethylcyclohexyl, etc. and The group after making them divalent groups.

Among them, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecanyl, n-heptadecanyl Alkyl, n-octadecyl, neopentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, cyclohexyl, cyclooctyl, 3, 5-Tetramethylcyclohexyl groups and groups after making them divalent groups.

As the above-mentioned alkenyl group and alkenylene group, a group having 2 to 16 carbon atoms is preferable, for example, vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butanyl group, etc. Alkenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylethenyl, 1,2-diphenylethenyl, 1-methylallyl , 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenyl aryl allyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, etc., and groups that make them divalent , preferably a styryl group, a 2,2-diphenylethenyl group, a 1,2-diphenylethenyl group, and a divalent group thereof.

The aralkyl group and aralkylene group are preferably groups having 7 to 18 carbon atoms, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenyl Isopropyl, 2-phenylisopropyl, phenyl-tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthyliso Propyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthylethyl, 2-β-naphthylethyl, 1-β-naphthylisopropyl, 2- β-naphthylisopropyl, 1-pyrrolylmethyl, 2-(1-pyrrolyl)ethyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxy Benzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group, etc., which have become divalent groups. Among them, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenyliso Propyl groups and the groups after making them divalent groups.

Examples of the hydrocarbon group containing the amino group or hydroxyl group include an amino group having each of the hydrocarbon groups represented by L ¹ to L ⁵ above, and a group in which a hydrogen atom of the hydrocarbon group is substituted with a hydroxyl group.

In the general formula (1), L is a ^heterocyclic ring with 3 to 30 ring carbon atoms which may also have a substituent, a carboxylate with 1 to 30 carbon atoms, a carboxylate with 1 to 30 carbon atoms which may also have a substituent Acid amide, an amine that may have a substituent, a phosphine that may have a substituent, an isocyanide that may have a substituent, an ether with a carbon number of 1 to 30 that may have a substituent, or a carbon number that may have a substituent A thioether of 1 to 30, or a double bond-containing compound having a carbon number of 1 to 30 which may have a substituent, and when L ⁵ and L ⁶ are cross-linked, they are monovalent groups of the respective compounds.

Examples of the heterocyclic ring include groups in which the same groups as those listed for L ¹ to L ⁵ above have a valence of zero.

As the carboxylic acid ester, for example, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl benzoate, ethyl benzoate, 2 -Methyl pyridinecarboxylate, ethyl 2-pyridinecarboxylate, methyl 3-pyridinecarboxylate, ethyl 3-pyridinecarboxylate, methyl 4-pyridinecarboxylate, ethyl 4-pyridinecarboxylate, phenylacetic acid Methyl ester, ethyl phenylacetate, methyl 2-pyridineacetate, ethyl 2-pyridineacetate, methyl 3-pyridineacetate, ethyl 3-pyridineacetate, methyl 4-pyridineacetate, ethyl 4-pyridineacetate , methyl 2-pyrrolecarboxylate, methyl 3-pyrrolecarboxylate, methyl 2-thiophenecarboxylate, methyl 3-thiophenecarboxylate, etc.

Examples of carboxylic acid amides include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbenzoic acid amide, N,N-dimethyl-2- Pyridinecarboxylic acid amide, N,N-dimethyl-3-pyridinecarboxylic acid amide, N,N-dimethyl-4-pyridinecarboxylic acid amide, N,N-dimethyl-phenylacetic acid amide, N, N-Dimethyl-2-pyridine acetic acid amide, N, N-dimethyl-3-pyridine acetic acid amide, N, N-dimethyl-4-pyridine acetic acid amide, N, N-dimethyl-2- Pyrrole carboxylic acid amide, N, N-dimethyl-3-pyrrole carboxylic acid amide, N, N-dimethyl-2-thiophene carboxylic acid amide, N, N-dimethyl-3-thiophene carboxylic acid amide, N-methylformamide, N-methylacetamide, N-methylbenzoic acid amide, N-methyl-2-pyridinecarboxylic acid amide, N-methyl-3-pyridinecarboxylic acid amide, N-methyl -4-pyridinecarboxylic acid amide, N-methyl-phenyl acetic acid amide, N-methyl-2-pyridine acetic acid amide, N-methyl-3-pyridine acetic acid amide, N-methyl-4-pyridine acetic acid amide , N-methyl-2-pyrrole carboxylic acid amide, N-methyl-3-pyrrole carboxylic acid amide, N-methyl-2-thiophene carboxylic acid amide, N-methyl-3-thiophene carboxylic acid amide, ethyl Amide, benzoic acid amide, 2-pyridine carboxylic acid amide, 3-pyridine carboxylic acid amide, 4-pyridine carboxylic acid amide, phenyl acetic acid amide, 2-pyridine acetic acid amide, 3-pyridine acetic acid amide, 4-pyridine acetic acid amide, 2-pyrrole carboxylic acid amide, 3-pyrrole carboxylic acid amide, 2-thiophene carboxylic acid amide, 3-thiophene carboxylic acid amide, etc.

As the amine, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, N,N-dimethylaniline, methyldiphenylamine, triphenylamine, dimethyl Base (2-pyridine) amine, dimethyl (3-pyridine) amine, dimethyl (4-pyridine) amine, methyl bis (2-pyridine) amine, methyl bis (3-pyridine) amine, methyl Bis(4-pyridine)amine, tris(2-pyridine)amine, tris(3-pyridine)amine, tris(4-pyridine)amine, diisopropylamine, di-n-propylamine, di-n-butylamine, N-methylaniline, methylphenylamine, diphenylamine, methyl(2-pyridine)amine, methyl(3-pyridine)amine, methyl(4-pyridine)amine, methyl(2-pyridine)amine ) amine, methyl (3-pyridine) amine, methyl (4-pyridine) amine, bis (2-pyridine) amine, n-propylamine, n-butylamine, aniline, (2-pyridine) amine, (3 -pyridine) amine, (4-pyridine) amine, (2-pyridine) amine, (3-pyridine) amine, (4-pyridine) amine, pyridine, 2-picoline, 3-picoline, 4-methyl Basepyridine, 2-trifluoromethylpyridine, 3-trifluoromethylpyridine, 4-trifluoromethylpyridine, N-methylpyrrole, etc.

Examples of the phosphine include groups in which the nitrogen of the amine is substituted with phosphorus, and the like.

Examples of the isonitrile include butyl isocyanide, isobutyl isocyanide, tert-butyl isocyanide, sec-butyl isocyanide, phenyl isocyanide, 2-tolyl isocyanide, 3-tolyl isocyanide compound, 4-tolyl isocyanide, 2-pyridine isocyanide, 3-pyridine isocyanide, 4-pyridine isocyanide, benzyl isocyanide, etc.

Examples of the ether include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-tert-butyl ether, anisole, diphenyl ether, Furan, tetrahydrofuran, dioxane, etc.

Examples of the thioether include groups in which the oxygen of the ether is substituted with sulfur.

Examples of the double bond-containing compound having 1 to 30 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -None, 1-decene, 1-eicosene, 2-butene, 2-pentene, 2-hexene, 2-heptene, 2-octene, 2-nonene, 2-decene , 2-eicosene, 3-hexene, 3-heptene, 3-octene, 3-nonene, 3-decene, 3-eicosene, isobutylene, styrene, α-methylbenzene Ethylene, β-methylstyrene, butadiene, isoprene, 1,2-stilbene, etc.

In addition, in the general formula (1), L ¹ and L ³ are preferably aromatic hydrocarbon groups or heterocyclic groups, for example, the structures shown below are preferable, among which phenyl and substituted phenyl are preferable. In addition, although Ir is illustrated as M in the following example, the example of the case other than Ir can also be mentioned. In addition, X represents an adjacent binding group, that is, L ² or L ⁴ .

[chemical 5]

In addition, in the general formula (1), when L ² and L ⁴ have carbene carbon, it is generally preferable to form a stable carbene with a metal, specifically, diaryl carbene, cyclic diamino carbon Alkene, imidazol-2-ylidene, 1,2,4-triazole-3-ylidene, 1,3-thiazol-2-ylidene, acyclic diaminocarbene, acyclic aminooxycarbene, Acyclic aminothiocarbene, cyclic dioxaboryl carbene, acyclic dioxaboryl carbene, phosphinated silyl carbene, phosphinophosphinocarbene, sulfenyl Trifluoromethylcarbene, sulfenyl pentafluorothiocarbene, etc. (reference Chem. Rev. 2000, 100, p39).

Among them, imidazol-2-ylidene, 1,2,4-triazole-3-ylidene, and cyclic diaminocarbene are preferred, and imidazol-2-ylidene and 1,2,4-triazole-3-ylidene are more preferred. 3-subunit, its specific structure is listed below. In addition, in the following examples, ring A represents an adjacent binding group, that is, L ¹ or L ³ .

[chemical 6]

In addition, preferred specific examples when L ² and L ⁴ are groups having no carbene carbon are listed below. In the following examples, the carbon bonded to ^L1 or ^L3 is preferably at the ortho position of the heteroatom that coordinates with the metal M, and the following examples may also be substituted.

[chemical 7]

In addition, in the general formula (1), preferred examples of L ⁵ include the same examples as those listed for L ¹ and L ³ . Among the examples described above, examples other than X are further preferred.

Preferable examples of ^L6 include a group containing a pyridine ring, a group containing a pyrrole ring, a group containing an imidazole ring, a group containing a pyrazole ring, a group containing a 1,2,3-triazole ring, Groups containing 1,2,4-triazole rings, groups containing thiophene rings, groups containing furan rings, groups containing oxazole rings, groups containing thiazole rings, R ¹⁸ ₃ N, R ¹⁹ ₃ P, C=NR ²⁰ , R ²¹ ₂ O, R ²² ₂ S, R ²³ R ²⁴ C=CR ²⁵ R ²⁶ , R ²⁷ COOR ²⁸ , R ²⁹ CONR ³⁰ R ³¹ (R ¹⁸ to R ³¹ Each independently, and the same example as the above-mentioned R ¹ and R ² can be mentioned, each can be the same or different, and can also be cross-linked.) group of the structure.

In addition, when ^L5 and ^L6 are cross-linked to form ^L5 - ^L6 , preferred examples of the above-mentioned ^L5 and ^L6 are cross-linked, and the above-mentioned ^L1 and ^L3 , the same examples as the preferred examples listed above for L ² and L ⁴ .

The transition metal complex represented by the general formula (1) of the present invention is preferably a transition metal complex having a metal carbene bond represented by the following general formula (2).

[chemical 8]

In the general formula (2), a bond indicated by a solid line represents a covalent bond, a bond represented by an arrow represents a coordinate bond, and at least one of L ² →M and L ⁴ →M represents a metal carbene bond. M and L ¹ to L ⁶ are the same as described above. L ¹ → L ² and L ³ → L ⁴ represent a cross-linked bidentate ligand, L ⁵ and L ⁶ each independently represent a monodentate ligand or a cross-linked bidentate ligand in which L ⁵ and L ⁶ have been cross-linked Bit (L ⁵ -L ⁶ ), L ¹ and L ³ , L ¹ and L ⁴ , L ² and L 3 , L ² and L ⁴ , L ¹ and L ⁵ , L ¹ and L ⁶ , L ^{2 and} L ^5. At least one of L ² and L ⁶ , L ³ and L ⁵ , L ³ and L ⁶ , L ⁴ and L ⁵ , and L ⁴ and L ⁶ via a crosslinking group -Z ¹ - (Z ¹ is the same as above) to cross-link.

In the general formula (2), n represents an integer of 0 to 1, and 2+n represents the atomic valence of the metal M. When n is plural, each of L ³ to L ⁴ may be the same or different, and adjacent groups may be cross-linked.

In the general formulas (1) and (2), (L ¹ -L ² )M and/or (L ³ -L ⁴ )M preferably has a structure represented by the following general formula (3).

[chemical 9]

In the general formula (3), C (carbon atom)→M represents a metal carbene bond, and M is the same as described above.

In the general formula (3), X is a nitrogen-containing group (-NR ¹ -), a phosphorus-containing group (-PR ¹ -), oxygen (-O-) or sulfur (-S-), and Y is a nitrogen-containing group (-NR ¹ R ² ), phosphorus-containing group (-PR ¹ ), oxygen-containing group (-OR ¹ ) or sulfur-containing group (-SR ¹ ), X and Y can also be cross-linked to form a ring structure.

Said R ¹ and R ² each independently represent 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 also have a substituent, or an alkyl group which may have a substituent An aromatic hydrocarbon group with 6 to 30 ring carbon atoms, a cycloalkyl group with 3 to 50 ring carbon atoms that may have a substituent, an aralkyl group with 7 to 40 carbon atoms that may also have a substituent, or a substituted An alkenyl group having 2 to 30 carbon atoms, a heterocyclic group having 3 to 30 ring atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may also have a substituent, or an alkoxy group having 1 to 30 carbon atoms which may also have a substituent An aryloxy group with 6 to 30 ring carbon atoms, an alkylamino group with 3 to 30 carbon atoms that may also have a substituent, an arylamino group with 6 to 30 carbon atoms that may also have a substituent, and a carbon group that may also have a substituent An alkylsilyl group having a number of 3 to 30, an arylsilyl group having a carbon number of 6 to 30 which may also have a substituent, a group containing a carboxyl group having a carbon number of 1 to 30 which may also have a substituent, ^R1 and ^R2 can also be crosslinked.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl , n-pentadecanyl, n-hexadecanyl, n-heptadecanyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentyl Hexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2 -Dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxytert-butyl, 1,2,3-trihydroxypropyl, aminomethyl, 1-aminoethyl, 2-amino Ethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl, 2,3-diaminotert-butyl, 1,2,3-triaminopropyl, Cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2, 3-dicyano-tert-butyl, 1,2,3-tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 1,2-dinitroethyl, 2,3-dinitro-tert-butyl, 1,2,3-trinitropropyl, cyclopentyl, cyclohexyl, cyclooctyl, 3,5-tetramethylcyclohexyl, etc.

Among them, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl are preferred , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecanyl, n-heptadecanyl Carbon alkyl, n-octadecyl, neopentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, cyclohexyl, cyclooctyl, 3 , 5-tetramethylcyclohexyl.

The haloalkyl group is preferably a group having 1 to 10 carbon atoms, such as chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1, 2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-tert-butyl, 1,2,3-trichloropropyl, bromomethyl, 1-bromo Ethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-tert-butyl , 1,2,3-tribromopropyl, iodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl, 1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-tert-butyl, 1,2,3-triiodopropyl, fluoromethyl, 1-fluoromethyl, 2-fluoro Methyl, 2-fluoroisobutyl, 1,2-difluoroethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, perfluoroisopropyl, perfluorobutyl, perfluorocyclic Hexyl etc.

Among them, fluoromethyl, trifluoromethyl, pentafluoroethyl, perfluoroisopropyl, perfluorobutyl, and perfluorocyclohexyl are preferred.

基、全氟代苯基等。The aromatic hydrocarbon group is preferably a group having 6 to 18 ring carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracene Base, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthalenyl, 2-naphthalenyl, 9-naphthalenyl, 1- Pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-triphenyl-4-yl, p-triphenyl-3-yl, p-triphenyl -2-yl, m-triphenyl-4-yl, m-triphenyl-3-yl, m-triphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl , p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-anthracenyl, 4'-methylbiphenyl Base, 4"-tert-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylylene, 3,4-xylylene, 2,5-Xylylene,

base, perfluorophenyl group, etc.

Among them, phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-tolyl, 3,4-xylylene Base etc.

Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 1-adamantyl, 2-adamantyl, and 1-norbornyl alkenyl, 2-norbornenyl, etc.

The aralkyl group is preferably a group having 7 to 18 carbon atoms, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2- Phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α -Naphthylisopropyl, β-naphthylmethyl, 1-β-naphthylethyl, 2-β-naphthylethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl Base, 1-pyrrolylmethyl, 2-(1-pyrrolyl)ethyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl Base, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group, etc. Among them, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenyliso Propyl.

The alkenyl group is preferably a group having 2 to 16 carbon atoms, for example, vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylethenyl, 1,2-diphenylethenyl, 1-methylallyl, 1,1- Dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, etc., preferably styryl, 2,2-diphenylethenyl, 1 , 2-diphenylethenyl.

The heterocyclic group is preferably a heterocyclic group having 3 to 18 ring atoms, for example, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridyl, 1 -imidazolyl, 2-imidazolyl, 1-pyrazolyl, 1-indoxazinyl, 2-indoxazinyl, 3-indoxazinyl, 5-indoxazinyl, 6-indoxazinyl, 7-indoxazinyl, 8-indoxazinyl, 2-imidazopyridyl, 3-imidazopyridyl, 5-imidazopyridyl, 6-imidazopyridyl, 7-imidazopyridyl, 8 -imidazopyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl Base, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuran Base, 7-benzofuryl, 1-isobenzofuryl, 3-isobenzofuryl, 4-isobenzofuryl, 5-isobenzofuryl, 6-isobenzofuryl, 7 -isobenzofuryl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1 -isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 8-isoquinolinyl, 2- Quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, β -carboline-1-yl, β-carboline-3-yl, β-carboline-4-yl, β-carboline-5-yl, β-carboline-6-yl, β-carboline-7 -yl, β-carboline-8-yl, β-carboline-9-yl, 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl , 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9 -Acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5 - Base, 1,7-phenanthroline-6-yl, 1,7-phenanthroline-8-yl, 1,7-phenanthroline-9-yl, 1,7-phenanthroline-10-yl , 1,8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl, 1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl, 1 , 8-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl, 1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl, 1,9 -Phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-yl, 1,9-phenanthroline Phenanthroline-6-yl, 1,9-phenanthroline-7-yl, 1,9-phenanthroline-8-yl, 1,9-phenanthroline-10-yl, 1,10-phenanthroline -2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 2,9-phenanthroline-1 - Base, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline-5-yl, 2,9-phenanthroline-6-yl , 2,9-phenanthrolin-7-yl, 2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl, 2,8-phenanthrolin-1-yl, 2 , 8-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl, 2,8-phenanthrolin-6-yl, 2,8 -Phenanthroline-7-yl, 2,8-phenanthroline-9-yl, 2,8-phenanthroline-10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline Phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-yl, 2,7-phenanthroline-6-yl, 2,7-phenanthroline -8-yl, 2,7-phenanthrolin-9-yl, 2,7-phenanthrolin-10-yl, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2- Phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phen Oxazinyl, 10-phenoxazinyl, 2-oxazolinyl, 4-oxazolinyl, 5-oxazolinyl, 2-oxadiazolinyl, 5-oxadiazolinyl, 3- Furazanyl, 2-thianthyl, 3-thianthyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl, 2-methyl Pyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl, 2-tert-butyl Basepyrrol-4-yl, 3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl- 3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indolyl, 4-tert-butyl-1-indolyl, 2-tert-butyl-3-indolyl Indolyl, 4-tert-butyl-3-indolyl, pyrrolidine, pyrazolidine, piperazine, etc.

Among them, 2-pyridyl, 1-indole azinyl, 2-indole azinyl, 3-indole azinyl, 5-indole azinyl, 6-indole azinyl, 7-indole azinyl, 8 -indoxazinyl, 2-imidazopyridyl, 3-imidazopyridyl, 5-imidazopyridyl, 6-imidazopyridyl, 7-imidazopyridyl, 8-imidazopyridyl, 3- Pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 1 -carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl.

The alkoxy group and aryloxy group are groups represented by -OX ¹ , and examples of X ¹ include the same examples as those described for the alkyl group, haloalkyl group, and aryl group.

The alkylamino group and the arylamino group are groups represented by -NX ¹ X ² , examples of X ¹ and X ² respectively include the examples described in the alkyl group, haloalkyl group, and aryl group Same example.

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

Examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldi Methylsilyl, etc.

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

In addition, examples of the ring structure formed by cross-linking X and Y include the same examples as those mentioned for the heterocyclic group.

In the general formula (3), as the carbene skeleton represented by -XCY (corresponding to L ² and L ⁴ ), it is preferable to include the case where L ² and L ⁴ in the general formula (1) have a carbene carbon The same example as the enumerated preferred examples.

In the general formula (3), Z is an atom forming a covalent bond with the metal M, which is a carbon, silicon, nitrogen or phosphorus atom, and the A ring containing Z is an aromatic ring with 3 to 40 ring carbon atoms that may also have substituents. An aromatic hydrocarbon group or an aromatic heterocyclic group having 3 to 40 ring atoms which may have a substituent.

Examples of the aromatic hydrocarbon group include the same examples as those mentioned above, and examples of the aromatic heterocyclic group include groups that are aromatic heterocyclic groups in the examples of the heterocyclic group described above.

Among them, as the ring A, in the general formula (1), the same preferred examples as those listed for L ¹ and L ³ can be preferably mentioned.

In addition, the compound represented by the general formula (1) or (2) is preferably a transition metal complex having a metal carbene bond represented by the following general formula (4).

[chemical 10]

In the general formula (4), C (carbon atom)→M represents a metal carbene bond. M represents a metal atom of iridium (Ir) or platinum (Pt). K represents an integer of 1 to 3, m represents an integer of 0 to 2, and k+m represents the atomic valence of the metal M. K+m

[chemical 11]

(Substituted) N-phenyl-N'-R ³ -imidazol-2-ylidene-C ² , C ² ' groups and

[chemical 12]

(Substituted) 2-phenylpyridine-N, at least two of the C ² ' groups are cross-linked via the cross-linking group -Z ¹ - (Z ¹ is the same as described above).

In the general formula (4), ^R3 is an alkyl group having 1 to 30 carbon atoms which may also have a substituent, a haloalkyl group having 1 to 30 carbon atoms which may also have a substituent, or a ring carbon atom number which may also have a substituent An aromatic hydrocarbon group of 6 to 30, a cycloalkyl group having 3 to 30 ring carbon atoms which may also have a substituent, an aralkyl group having 7 to 40 carbon atoms which may also have a substituent, a carbon number which may also have a substituent An alkenyl group of 2 to 30, a heterocyclic group having 3 to 30 ring atoms which may have a substituent, an alkylsilyl group having 3 to 30 ring atoms which may also have a substituent, or an optionally substituted An arylsilyl group having 6 to 30 carbons, a carboxyl group containing 1 to 30 carbons.

In the general formula (4), R ⁴ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom (fluorine, bromine, iodine, chlorine, etc.), a thiocyano group or a cyano group, a nitro group, -S(=O) ₂ R ¹ group or -S(=O)R ¹ (R ¹ is the same as above), an alkyl group having 1 to 30 carbon atoms which may have a substituent, a haloalkyl group having 1 to 30 carbon atoms which may also have a substituent, Aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may also have substituents, cycloalkyl group having 3 to 30 ring carbon atoms which may also have substituents, arane having 7 to 40 carbon atoms which may also have substituents group, an alkenyl group having 2 to 30 carbon atoms which may also have a substituent, a heterocyclic group having 3 to 30 ring atoms which may also have a substituent, an alkoxy group having 1 to 30 carbon atoms which may also have a substituent , an aryloxy group with 6 to 30 ring carbon atoms that may also have a substituent, an alkylamino group with 3 to 30 ring atoms that may also have a substituent, an alkyl group with 3 to 30 ring atoms that may also have a substituent A silyl group, an arylsilyl group having 6 to 30 carbon atoms that may have a substituent, a carboxyl group having 1 to 30 carbon atoms, R ⁴ to R ¹⁷ may also be crosslinked between adjacent groups .

As the alkyl group, haloalkyl group, aromatic hydrocarbon group, cycloalkyl group, aralkyl group, alkenyl group, heterocyclyl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsilyl group Specific examples of the arylsilyl group and the carboxyl group-containing group include the same examples as R ¹ and R ² in the general formula (3).

Among the general formula (4), a transition metal complex represented by the following general formula (5) in which M is Ir is particularly preferable.

[chemical 13]

In the general formula (5), C (carbon atom)→Ir represents a metal carbene bond. K, m, and R ³ to R ¹⁷ are the same as described above. K+m (substituted) N-phenyl-N'-R ³ -imidazol-2-ylidene-C ² , C ² 'base, and (substituted) 2-phenylpyridine-N, C ² ' base At least two of them are cross-linked via a cross-linking group -Z ¹ - (Z ¹ is the same as described above).

Examples of substituents for each of the groups in the general formulas (1) to (5) include substituted or unsubstituted aryl groups having 5 to 50 ring carbon atoms, substituted or unsubstituted aryl groups having 1 to 50 carbon atoms, 50 alkyl, substituted or unsubstituted alkoxy with 1 to 50 carbon atoms, substituted or unsubstituted aralkyl with 6 to 50 ring carbon atoms, substituted or unsubstituted aralkyl with 5 to 50 ring carbon atoms Aryloxy group, substituted or unsubstituted arylthio group with 5 to 50 ring carbon atoms, substituted or unsubstituted alkoxycarbonyl group with 1 to 50 carbon atoms, amino group, halogen atom, cyano group, nitro group, Hydroxyl, carboxyl, etc.

Among them, an alkyl group with 1 to 10 carbons, a cycloalkyl group with 5 to 7 carbons, an alkoxy group with 1 to 10 carbons are preferred, an alkyl group with 1 to 6 carbons is more preferred, and a ring with 5 to 7 carbons is more preferred. Alkyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl.

Next, an example of the production method of the transition metal complex compound of the general formula (1) of the present invention will be described below.

1. the synthetic method of the transition metal coordination compound of general formula (5) (k=3, m=0)

[chemical 14]

2. the synthetic method of the transition metal coordination compound of general formula (5) (k=2, m=1)

[chemical 15]

In the above-mentioned Examples 1 and 2, the ligands may be added twice (arbitrary order) and synthesized in two stages.

Next, the general formula (6) will be described.

[chemical 16]

In general formula (6), A represents the cross-linked bidentate ligand group formed by L ¹¹ -(Z ¹¹ ) _d -L ¹² , and B represents the cross-linked group formed by L ¹³ -(Z ¹² ) _e -L ¹⁴ A bidentate ligand group, and C represents a cross-linked bidentate ligand group formed by L ¹⁵ -(Z ¹³ ) _f -L ¹⁶ . L ¹¹ -, L ¹³ - and L ¹⁵ - represent covalent bonds with Ir (iridium) respectively (L ¹¹ -Ir, L ¹³ -Ir and L ¹⁵ -Ir), L ¹² →, L ¹⁴ → and L ¹⁶ → Each represents a coordination bond with Ir (iridium) (L ¹² →Ir, L ¹⁴ →Ir, and L ¹⁶ →Ir).

In the general formula (6), ^X1 is a crosslinking group formed by an acyclic structure with an atomic number of 1 to 18, and is selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, The trivalent residue of the compound composed of the phosphorus atom and the boron atom may have a substituent.

As such ^X1, any of the following structures can be mentioned,

[chemical 17]

The following structures are preferred,

[chemical 18]

The following structures are further preferred.

[chemical 19]

As R, the same examples as ^R can be mentioned, preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, ethoxy group, etc., more preferably hydrogen atom, methyl group, ethyl group, tert-butyl group, phenyl group.

In general formula (6), Y ¹ represents the cross-linking group combining X and A, Y ² represents the cross-linking group combining X and B, Y ³ represents the cross-linking group combining X and C, Y ¹ and L ¹¹ , L ¹² or Z ¹¹ , Y ² is combined with L ¹³ , L ¹⁴ or Z ¹² , Y ³ is combined with L ¹⁵ , L ¹⁶ or Z ¹³ . Y ¹ , Y ² and Y ³ each independently represent a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, It may also have a substituent.

In general formula (6), a, b, and c each independently represent an integer of 0-10, preferably 0-3. When a, b or c is plural, a plurality of Y ¹ , Y ² or Y ³ may be the same or different.

Specific examples of Y ¹ , Y ² and Y ³ include -CR ¹ R ² -, -SiR ¹ R ² -, -NR ¹ -, -O-, -S-, -PR ¹ - and -BR ¹ - etc. R ¹ and R ² are the same as described above, and may be the same or different. In addition, R1 and R2 may be cross-linked with X, or may be cross-linked between ^R1 and ^R2 . When a, b and c are plural, each Y ¹ , each Y ² and each Y ³ can be arbitrarily selected from -CR ¹ R ² -, -SiR ¹ R ² -, -NR ¹ -, -O-, -S -, -PR ¹ - and -BR ¹ - to choose from. In addition, at this time, R ¹ and R ² between each Y ¹ , each Y ² and each Y ³ may be cross-linked with X, or may be cross-linked between R ¹ and R ² .

Preferable specific structures of Y ¹ , Y ² and Y ³ include, for example, -CH ₂ -, -CMe ₂ -, -CMeH-, -CEtH-, -O-, -S-, -SiH ₂ -, -SiMe ₂ -, -SiMeH-, -SiEtH-, -NH-, -NMe-, -NEt-, -PH-, -PMe-, -PEt-, -BH-, -BMe-, -BEt-(Me is methyl, Et is ethyl) and so on.

In general formula (6), Z ¹¹ represents the cross-linking group combining L ¹¹ and L ¹² , Z ¹² represents the cross-linking group combining L ¹³ and L ¹⁴ , Z ¹³ represents the cross-linking group combining L ¹⁵ and L ¹⁶ , Z ¹¹ , ^Z12, and ^Z13 each independently represent a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, and May have a substituent. When Z ¹¹ is directly bonded to Y ¹ , when Z ¹² is directly bonded to Y ² , or when Z ¹³ is directly bonded to Y ³ , Z ¹¹ , Z ¹² and Z ¹³ become corresponding trivalent groups, respectively.

In general formula (6), d, e, and f each independently represent an integer of 0-10, preferably 0-3. When d, e or f is a plural number, a plurality of Z ¹¹ , Z ¹² or Z ¹³ may be the same or different.

In the general formula (6), L ¹¹ , L ¹³ and L ¹⁵ each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 3 to 30 ring carbon atoms which may also have a substituent. A divalent heterocyclic group of 30, a divalent carboxyl-containing group having 1 to 30 carbon atoms that may have a substituent, a divalent amino- or hydroxyl-containing hydrocarbon group that may also have a substituent, or a hydrocarbon group that may have a substituent A cycloalkylene group having 3 to 50 ring carbon atoms, an alkylene group having 1 to 30 carbon atoms which may have a substituent, an alkenylene group having 2 to 30 carbon atoms which may also have a substituent, or an alkenylene group having 2 to 30 carbon atoms which may also have a substituent C7-40 aralkylene, when L ¹¹ is directly combined with Y ¹ , when L ¹³ is directly combined with Y ² , or when L ¹⁵ is directly combined with Y ³ , L ¹¹ , L ¹³ and L ¹⁵ become the corresponding trivalent groups respectively.

Examples of these divalent aromatic hydrocarbon groups, divalent heterocyclic groups, divalent carboxyl group-containing groups, cycloalkylene groups, alkylene groups, alkenylene groups, and aralkylene groups include the following: Examples of aromatic hydrocarbon groups, heterocyclic groups, carboxyl-containing groups, cycloalkyl groups, alkyl groups, alkenyl groups, and aralkyl groups described by R ^a to R ⁱ are divalent groups, and preferred groups are also The same group can be mentioned.

In addition, examples of divalent hydrocarbon groups containing an amino group or a hydroxyl group include amino groups having the hydrocarbon groups represented by L ¹¹ , L ¹³ , and L ¹⁵ , and groups in which the hydrogen atoms of the hydrocarbon groups are substituted by hydroxyl groups. .

In addition, the L ¹¹ , L ¹³ and L ¹⁵ are preferably aromatic hydrocarbon groups or heterocyclic groups, for example, the structures shown below are preferable, among which phenyl and substituted phenyl are preferable. In addition, in the following examples, Y represents an adjacent binding group, that is, L ¹² , L ¹⁴ or L ¹⁶ .

[chemical 20]

In the general formula (6), L ¹² , L ¹⁴ and L ¹⁶ each independently represent a monovalent group having a carbene carbon which may have a substituent, or a 1 having 3 to 30 ring atoms which may also have a substituent. When L ¹² is directly combined with Y ¹ , when L ¹⁴ is directly combined with Y ² , or when L ¹⁶ is directly combined with Y ³ , L ¹² , L ¹⁴ and L ¹⁶ become the corresponding divalent group. At least one of L ¹² , L ^{14 and} L ¹⁶ is preferably a group having carbene carbon, and it is more preferable that L ¹² , L ¹⁴ and L ¹⁶ are groups having carbene carbon.

In addition, as a monovalent group having a carbene carbon, a group that forms a stable carbene together with a metal is generally preferable, and specifically, diarylcarbene, cyclic diaminocarbene, imidazole-2 -ylidene, 1,2,4-triazole-3-ylidene, 1,3-thiazol-2-ylidene, acyclic diaminocarbene, acyclic aminooxycarbene, acyclic aminothio Carbene, cyclic dioxaboryl carbene, acyclic dioxaboryl carbene, phosphinated silyl carbene, phosphinated phosphine carbene, sulfenyl trifluoromethyl carbene, Monovalent groups such as oxythiopentafluorothiocarbene (reference: Chem. Rev. 2000, 100, p39).

Among them, imidazol-2-ylidene, 1,2,4-triazole-3-ylidene, and cyclic diaminocarbene are preferred, and imidazol-2-ylidene and 1,2,4-triazole-3-ylidene are more preferred. 3-subunit, its specific structure is listed below. In addition, in the following examples, ring A represents an adjacent binding group, that is, L ¹¹ , L ¹³ or L ¹⁵ . R ^j is the same as R ¹ and R ² described above.

[chem 21]

In addition, preferred specific examples when L ¹² , L ¹⁴ and L ¹⁶ are groups having no carbene carbon, that is, examples of heterocyclic groups are listed below. In the following examples, the carbon bonded to L ¹¹ , L ¹³ or L ¹⁵ is preferably in the ortho position of the heteroatom that coordinates with iridium, and the following examples may also be substituted.

[chem 22]

The sum of the atomic weights constituting the following crosslinking sites (7) in the general formula (6) is preferably 200 or less, more preferably 100 or less.

When the sum of the atomic weights of the cross-linking sites (7) is reduced, if the A, B, and C sites in the general formula (6) are the same, the molecular weight of the coordination compound will decrease, and the reduction is equivalent to the cross-linking amount. The reduced amount of the sum of the atomic weights of the linking sites (7) is therefore advantageous in maintaining high purity during the sublimation process at the time of manufacturing an organic EL element. Therefore, by reducing the total atomic weight of the crosslinking sites, there is an effect of improving the purity of the coordination compound or the purity of the organic EL device.

[chem 23]

Examples of substituents for each group in the general formula (6) include a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, Substituted or unsubstituted alkoxy group with 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group with 6 to 50 ring carbon atoms, substituted or unsubstituted aryloxy group with 5 to 50 ring carbon atoms, substituted Or an unsubstituted arylthio group with 5 to 50 ring carbon atoms, a substituted or unsubstituted alkoxycarbonyl group with 1 to 50 carbon atoms, amino group, halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, etc.

Among them, an alkyl group with 1 to 10 carbons, a cycloalkyl group with 5 to 7 carbons, an alkoxy group with 1 to 10 carbons are preferred, an alkyl group with 1 to 6 carbons is more preferred, and a ring with 5 to 7 carbons is more preferred. Alkyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl.

Next, the manufacturing process as an example of the manufacturing method of the transition metal complex compound of general formula (6) of this invention is shown below. (References: JACS 96, 16, 1974, p5189)

[chem 24]

[chem 25]

Ligand A Ligand B

Coordination compound A Coordination compound B

In the organic EL element of the present invention, an organic thin film layer composed of one or more layers having at least a light-emitting layer is sandwiched between a pair of electrodes composed of an anode and a cathode, wherein at least one of the organic thin layers contains the transition metal complexes. It is preferred to contain transition metal coordination compounds represented by any one of general formulas (1), (2), (4), (5) and (6), and more preferably to contain transition metal complexes of general formulas (4) or (5). metal complexes.

The content of the metal complex compound of the present invention in the organic thin film layer is usually 0.1 to 100% by weight, preferably 1 to 30% by weight, based on the mass of the entire light emitting layer.

In the organic EL device of the present invention, it is preferable that the light-emitting layer contains the transition metal complex of the present invention as a light-emitting material or a dopant. In addition, the light-emitting layer is usually thinned by vacuum deposition or coating, but from the viewpoint that coating can simplify the production process, it is preferable that the layer containing the transition metal complex of the present invention is formed by coating. .

In the organic EL device of the present invention, if the organic thin film layer is a single-layer type, the organic thin film layer is a light emitting layer, and the light emitting layer contains the transition metal complex of the present invention. In addition, examples of multilayer organic EL elements include (anode/hole injection layer (hole transport layer)/light-emitting layer/cathode), (anode/light-emitting layer/electron injection layer (electron transport layer)/cathode ), (anode/hole injection layer (hole transport layer)/light emitting layer/electron injection layer (electron transport layer)/cathode), etc.

The anode of the organic EL element of the present invention supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like, and an anode having a work function of 4.5 eV or more is effective. As the material of the anode, metals, alloys, metal oxides, conductive compounds, or mixtures thereof can be used. Specific examples of anode materials include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and conductive metal oxides such as these. Mixtures or laminates of oxides and metals, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and their laminates with ITO, etc., preferably conductive metal oxides In particular, ITO is preferably used from the viewpoints of productivity, high conductivity, and transparency. The film thickness of the anode can be appropriately selected according to the implementation.

The cathode of the organic EL element of the present invention supplies electrons to the electron injection layer, electron transport layer, light emitting layer, etc., and as the material of the cathode, metals, alloys, metal halides, metal oxides, conductive compounds, or mixtures thereof can be used. . As specific examples of cathode materials, alkali metals (for example, Li, Na, K, etc.) and their fluorides or oxides, alkaline earth metals (for example, Mg, Ca, etc.) and their fluorides or oxides, Gold, silver, lead, aluminum, sodium-potassium alloy or sodium-potassium mixed metal, lithium-aluminum alloy or lithium-aluminum mixed metal, magnesium-silver alloy or magnesium-silver mixed metal, or rare earth metals such as indium and ytterbium, etc. . Among them, aluminum, lithium-aluminum alloy or lithium-aluminum mixed metal, magnesium-silver alloy or magnesium-silver mixed metal, etc. are preferable. The cathode may have a single-layer structure of the above-mentioned material, or may have a laminated structure of layers including the above-mentioned material. For example, a laminated structure of aluminum/lithium fluoride and aluminum/lithium oxide is preferable. The film thickness of the cathode can be appropriately selected according to the material.

The hole injection layer and the hole transport layer of the organic EL device of the present invention may have any function of injecting holes from the anode, transporting holes, and blocking electrons injected from the cathode. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyaryl alkane derivatives, pyrazoline derivatives, pyrazole Ketone derivatives, phenylenediamine derivatives, aromatic amine derivatives, amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, Aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethyl compounds, porphyrin compounds, polysilane compounds, poly(N-vinylcarbazole) derivatives, aniline copolymers, thiophene low Polymers, conductive polymer oligomers such as polythiophene, organosilane derivatives, transition metal complexes of the present invention, and the like. In addition, the hole injection layer and the hole transport layer may be a single-layer structure composed of one or more than two kinds of materials, or may be a multi-layer structure composed of multiple layers of the same or different compositions. layer structure.

The electron injection layer and the electron transport layer of the organic EL device of the present invention may have any function of injecting electrons from the cathode, transporting electrons, and blocking holes injected from the anode. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinone dimethane derivatives, anthrone derivatives, diphenylbenzoquinone derivatives, Derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyryl pyrazine derivatives, naphthalene, perylene and other aromatic ring tetracarboxylic anhydrides, phthalocyanine derivatives, 8 - Metal complexes of hydroxyquinoline derivatives, various metal complexes represented by metal complexes using metal phthalocyanine, benzoxazole and benzothiazole as ligands, organosilane derivatives , the transition metal complex of the present invention, and the like. In addition, the electron injection layer and the electron transport layer may be a single-layer structure composed of one or two or more of the above-mentioned materials, or may be a multi-layer structure composed of multiple layers of the same or different compositions. .

Moreover, the following compounds are mentioned as an electron transport material used for an electron injection layer and an electron transport layer.

[chem 26]

[chem 27]

[chem 28]

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

Preferred examples of the π-electron-deficient nitrogen-containing heterocyclic derivatives include those selected from benzimidazole rings, benzotriazole rings, pyridimidazole rings, pyrimidimidazole rings, and pyridazinoimidazole rings. Nitrogen-containing five-membered ring derivatives, and nitrogen-containing six-membered heterocyclic derivatives composed of pyridine ring, pyrimidine ring, pyrazine ring and triazole ring, as nitrogen-containing five-membered ring derivatives, the following general formula The preferred structure shown in B-I, and as nitrogen-containing six-membered ring derivatives, the preferred structures shown in the following general formulas C-I, C-II, C-III, C-IV, C-V and C-VI, especially The structures represented by general formulas C-I and C-II are preferred.

[chem 29]

In the general formula (BI), ^LB represents a linking group with a valence of more than two, preferably a linking group formed by carbon, silicon, nitrogen, boron, oxygen, sulfur, metal, metal ions, etc., more preferably a carbon atom, a nitrogen atom, Silicon atom, boron atom, oxygen atom, sulfur atom, aromatic hydrocarbon ring, aromatic heterocyclic ring, particularly preferably carbon atom, silicon atom, aromatic hydrocarbon ring, aromatic heterocyclic ring.

L ^B may also have a substituent, and the substituent is preferably an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, aromatic heterocycle group, more preferably alkyl, aryl, alkoxy, aryloxy, halogen atom, cyano, aromatic heterocyclic group, more preferably alkyl, aryl, alkoxy, aryloxy, aromatic heterocyclic group, particularly preferably an alkyl group, an aryl group, an alkoxy group, and an aromatic heterocyclic group.

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

[chem 30]

In the general formula (BI), X ^B2 represents -O-, -S- or =NR ^B2 . R ^B2 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group.

The aliphatic hydrocarbon group represented by R ^B2 is a linear, branched or cyclic alkyl group (preferably a carbon number of 1 to 20, more preferably a carbon number of 1 to 12, particularly preferably a carbon number of 1 to 8, for example, Such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl (preferably carbon number 2 to 20, more preferably 2 to 12 carbons, particularly preferably alkenyls with 2 to 8 carbons, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkyne group (preferably C2-20, more preferably C2-12, particularly preferably C2-8 alkynyl, examples include propynyl, 3-pentynyl, etc.), more preferably alkyl.

The aryl group represented by R ^B2 is a monocyclic or condensed ring aryl group, preferably with 6 to 30 carbons, more preferably with 6 to 20 carbons, and even more preferably with 6 to 12 carbons, such as phenyl, 2 -Methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-trifluoromethylphenyl, pentafluorophenyl, 1-naphthyl, 2-naphthalene Base etc.

The heterocyclic group represented by R ^B2 is a monocyclic or condensed ring heterocyclic group (preferably a heterocyclic group with 1 to 20 carbons, more preferably a heterocyclic group with 1 to 12 carbons, and more preferably a heterocyclic group with 2 to 10 carbons), preferably containing a nitrogen atom, An aromatic heterocyclic group having at least one atom among an oxygen atom, a sulfur atom, and a selenium atom, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, selenophene, furan, pyrrole, imidazole, pyrazole, Pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline , phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotri Azole, tetrazaindene, carbazole, azepine, etc., among which furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline are preferred , more preferably furan, thiophene, pyridine, quinoline, more preferably quinoline.

The aliphatic hydrocarbon group, aryl group, and heterocyclic group represented by R ^B2 may have a substituent, and examples thereof include the same groups as those for L ^B described above.

R ^B2 is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably an aryl group, or an aromatic heterocyclic group, and even more preferably an aryl group.

X ^B2 is preferably -O-, =NR ^B2 , more preferably =NR ^B2 , particularly preferably =N-Ar ^B2 (Ar ^B2 is an aryl group (preferably carbon number 6-30, more preferably carbon number 6-20, more preferably carbon number 6-12 aryl), aromatic heterocyclic group (preferably 1-20 carbons, more preferably 1-12 carbons, still more preferably 2-10 carbons, aromatic heterocyclic group), preferably aryl).

Z ^B2 represents a group of atoms required to form an aromatic ring. The aromatic ring formed by Z ^B2 may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Specific examples thereof include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazole ring. , pyrrole ring, furan ring, thiophene ring, selenophene ring, tellurophene ring, imidazole ring, thiazole ring, selenazole ring, tellurazole ring, thiadiazole ring, oxadiazole ring, pyrazole ring, etc., among which, preferred Benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, more preferably benzene ring, pyridine ring, pyrazine ring, still more preferably benzene ring, pyridine ring, especially preferably pyridine ring. The aromatic ring formed from Z ^B2 may form a condensed ring with another ring and may have a substituent. As substituents, alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonyl are preferred Acylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, heterocyclic group, etc. Among them, alkyl, Aryl, alkoxy, aryloxy, halogen atom, cyano, heterocyclic group; more preferably alkyl, aryl, alkoxy, aryloxy, heterocyclic, especially preferably alkyl, aryl, alkane Oxygen, aromatic heterocyclic group.

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

Among the compounds represented by the general formula (B-I), compounds represented by the following general formula (B-II) are more preferred.

[chem 31]

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

Z ^B71 , Z ^B72 and Z ^B73 are respectively the same as Z ^B2 in the general formula (BI), and their preferred ranges are also the same.

L ^B71 , L ^B72 , and L ^B73 each represent a linking group, and examples of L ^B in the general formula (BI) are divalent. Among them, a single bond, a divalent aromatic hydrocarbon ring group, and a divalent aromatic hydrocarbon ring group are preferred. A divalent aromatic heterocyclic group and a linking group formed by a combination thereof are more preferably a single bond. L ^B71 , L ^B72 , and L ^B73 may have a substituent, and examples of the substituent include the same groups as those for L ^B in the general formula (BI).

Y represents a nitrogen atom, 1,3,5-benzenetriyl or 2,4,6-triazinetriyl. The 1,3,5-benzenetriyl group may have a substituent at the 2,4,6-position, and examples of the substituent include an alkyl group, an aromatic hydrocarbon ring group, a halogen atom, and the like.

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

[chem 32]

[chem 33]

[wherein, Cz is a substituted or unsubstituted carbazolyl, arylcarbazolyl, or carbazolylalkylene, and A is a group formed at a site represented by the following general formula (A). n and m are integers of 1-3, respectively.

(M)p-(L)q-(M’)r (A)

(M and M' each independently represent a nitrogen-containing aromatic ring with 2 to 40 carbon atoms forming a ring, and the ring may or may not have a substituent. In addition, M and M' may be the same or different. L is A single bond, an arylene group having 6 to 30 carbons, a cycloalkylene group having 5 to 30 carbons, or a heteroaromatic ring having 2 to 30 carbons may have a substituent bonded to the ring or may not have a substituent.p is an integer of 0 to 2, q is an integer of 1 to 2, and r is an integer of 0 to 2. Among them, p+r is 1 or more.)]

The combination of the general formulas (C-I) and (C-II) can be specifically expressed as described in the following table according to the values of the parameters n and m.

[Table 1]

In addition, the bonding mode of the group represented by the general formula (A) is specifically the form described in (1) to (16) in the following table according to the values of the parameters p, q, and r.

[Table 2]

[table 3]

In the general formulas (C-I) and (C-II), when Cz is bound to A, it may be bound to any part representing M, L, or M' of A. For example, if it is Cz-A with m=n=1, then in the case of p=q=r=1 ((6) in the table), A becomes M-L-M', and Cz-M-L-M' can be , M-L(-Cz)-M', M-L-M'-Cz are represented by three combinations. In addition, for example, in the general formula (C-I), if it is Cz-A-Cz of n=2, then in the case of p=q=1, r=2 ((7) in the table), A becomes M-L -M'-M' or M-L(-M')-M' can be represented by the following combinations.

[chem 34]

Specific examples of the general formulas (C-I) and (C-II) include the following structures, but are not limited thereto.

[chem 35]

[chem 36]

(In the formula, Ar ₁₁ to Ar ₁₃ respectively represent the same groups as R ^B2 in the general formula (BI), and the specific examples are also the same, and Ar ₁ to Ar ₃ represent the same groups as R ^B2 in the general formula (BI). The group after the group becomes divalent, and its specific examples are also the same.)

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

[chem 37]

[chem 38]

(In the formula, R ₁₁ to R ₁₄ 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-IV) are shown below, but are not limited thereto.

[chem 39]

[chemical 40]

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

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

[chem 41]

[chem 42]

(C-VI)

(In the formula, Ar ¹ to Ar ⁴ each represent the same group as R ^B2 in the general formula (BI), and the specific examples thereof are also the same.)

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

[chem 43]

In addition, in the organic EL device of the present invention, it is preferable to use an inorganic compound that is an insulator or a semiconductor as a substance constituting the electron injection/transport layer. If the electron injection/transport layer is made of an insulator or a semiconductor, the leakage of current can be effectively prevented and the electron injection property can be improved. As such an insulator, at least one metal compound selected from alkali metal chalcogen compounds, alkaline earth metal chalcogen compounds, alkali metal halides, and alkaline earth metal halides is preferably used. If the electron injection/transport layer is composed of these alkali metal chalcogen compounds, etc., it is preferable because the electron injection property can be further improved.

Specifically, examples of preferable alkali metal chalcogen compounds include Li ₂ O, LiO, Na ₂ S, Na ₂ Se, and NaO, and examples of preferable alkaline earth metal chalcogen compounds include , such as CaO, BaO, SrO, BeO, BaS, and CaSe. Moreover, as a preferable alkali metal halide, LiF, NaF, KF, LiCl, KCl, NaCl etc. are mentioned, for example. In addition, examples of halides of preferable alkaline earth metals include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , and BeF ₂ , and halides other than fluorides.

In addition, examples of semiconductors constituting the electron injection/transport layer include those containing at least one of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. A substance such as an oxide, nitride or oxynitride of one element or a combination of two or more substances. in addition. As the inorganic compound constituting the electron transport layer, a microcrystalline or amorphous insulating thin film is preferable. If the electron transport layer is composed of these insulating thin films, since a more uniform thin film is formed, pixel defects such as black spots can be reduced. In addition, examples of such inorganic compounds include the above-mentioned alkali metal chalcogen compounds, alkaline earth metal chalcogen compounds, alkali metal halides, alkaline earth metal halides, and the like.

In addition, 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 improves electron injection efficiency.

In addition, in the present invention, it is preferable to add a reducing dopant to the interface region between the cathode and the organic thin film layer to reduce and anionize at least a part of the organic layer contained in the interface region. Preferred reductive dopants are selected from alkali metals, alkaline earth metal oxides, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metal oxides or At least one compound selected from rare earth metal halides, alkali metal complexes, alkaline earth metal complexes and rare earth metal complexes. More specifically, as a preferable reductive dopant, it can be mentioned that Na (work function: 2.36eV), K (work function: 2.28eV), Rb (work function: 2.16eV) and Cs (work function: 2.16eV) and Cs (work function: : 1.95eV), and at least one alkaline earth selected from Ca (work function: 2.9eV), Sr (work function: 2.0-2.5eV) and Ba (work function: 2.52eV) Metals and the like, particularly preferably metals having a work function of 2.9 eV. Among them, the more preferred reducing dopant is at least one alkali metal selected from K, Rb and Cs, more preferably Rb or Cs, most preferably Cs. These alkali metals have particularly high reducing power, and adding a small amount to the electron injection region can improve the luminance of the organic EL device and achieve a longer life.

Examples of the alkaline earth metal oxides include BaO, SrO, CaO, and _{BaxSr1 -xO} (0<x<1) or _{BaxCa1 -} xO obtained by mixing them. (0<x<1). LiF, _Li2O , NaF etc. are mentioned as an alkali metal oxide or an alkali metal fluoride. The alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as the metal ion contains at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions. Examples of ligands include hydroxyquinoline, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydi Aryloxadiazole, hydroxydiarylthiadiazole, hydroxydiphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfluborane, bipyridine, phenanthroline, phthalocyanine, porphyrin, cyclic Pentadiene, β-diketones, formimines and their derivatives, etc., but not limited to these.

As a preferable form of the reducing dopant, a layered or island shape can be formed. The preferable film thickness when employing a layered form is 0.05 to 8 nm.

As a method for forming an electron injection/transport layer containing a reducing dopant, it is preferable to simultaneously vapor-deposit an organic substance which itself is a light-emitting material or an electron injection material forming an interface region while vapor-depositing a reducing dopant by a resistance heating vapor deposition method. , A method of dispersing reductive dopants in organic matter. As the dispersion concentration, the molar ratio is 100:1 to 1:100, preferably 5:1 to 1:5. When the reductive dopant is formed into a layer, after forming the luminescent material or the electron injection material as the interface organic layer in a layer, the reductive dopant is evaporated separately by the resistance heating evaporation method, preferably at a thickness of 0.5 nm. ~15nm film thickness is formed. When the reductive dopant is formed into an island shape, after forming the luminescent material or electron injection material as the interface organic layer, the reductive dopant is evaporated separately by the resistance heating evaporation method, preferably at a thickness of 0.05 to 1 nm. film thickness is formed.

The light-emitting layer of the organic EL element of the present invention has the following functions, that is, when an electric field is applied, holes can be injected from the anode or the hole injection layer, and the function of electrons can be injected from the cathode or the electron injection layer. The function of moving the injected charges (electrons and holes), and the function of providing a place for electrons and holes to recombine to make them emit light. The light-emitting layer of the organic EL device of the present invention preferably contains at least the transition metal complex of the present invention, and may contain a host material using such a transition metal complex as a guest material. Examples of the host material include materials having a carbazole skeleton, materials having a diarylamine skeleton, materials having a pyridine skeleton, materials having a pyrazine skeleton, materials having a triazine skeleton, and materials having an arylamine skeleton. Silane skeleton materials, etc. Preferably, the T1 (lowest triplet excited state energy level) of the host material is larger than the T1 level of the guest material. The host material can be either a low-molecular compound or a high-molecular compound. In addition, a light-emitting layer in which the light-emitting material is doped into the host material can be formed by co-evaporating the host material and the light-emitting material such as the transition metal complex.

In the organic EL element of the present invention, the formation method of each layer is not particularly limited, and vacuum evaporation method, LB method, resistance heating evaporation method, electron beam method, sputtering method, molecular lamination method, coating method, etc. can be used. method (spin coating method, casting method, dip coating method, etc.), inkjet method, printing method, etc., but the coating method is preferred in the present invention.

In addition, the organic thin film layer containing the transition metal complex of the present invention can be vacuum deposition method, molecular beam deposition method (MBE method), or coating method after dissolving in a solvent to prepare a solution, spin coating method, Formation by known methods such as casting, bar coating, and roll coating.

In the coating method, it can be formed by dissolving the transition metal complex of the present invention in a solvent to prepare a coating solution, applying the coating solution on a desired layer (or electrode), and drying it. A resin may be contained in the coating solution, and the resin may be in a state of being dissolved in a solvent or in a dispersed state. As the resin, non-conjugated polymers (eg, polyvinylcarbazole) and conjugated polymers (eg, polyolefin-based polymers) can be used. More specifically, examples include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene , poly(N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin , Alkyd resin, epoxy resin, silicone resin, etc.

In addition, although the film thickness of each organic layer of the organic EL element of the present invention is not particularly limited, if the film thickness is too thin, defects such as pinholes are likely to occur, and if it is too thick, a high voltage needs to be applied, so the efficiency deteriorates. Preferably, it is usually in the range of several nanometers to 1 micrometer.

Example

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

Embodiment 1 (synthesis of transition metal coordination compound 1)

(i) Synthesis of cross-linked ligand precursor (compound a)

The crosslinking ligand precursor (compound a) was synthesized by the following reaction procedure.

[chem 44]

Add 100ml tetrahydrofuran (THF) in 5.00g N-phenylimidazole (molecular weight 144.18, 34.7 mmol) and 5.05g of 1,4-diiodobutane (molecular weight 309.92, 16.3 mmol), stir at room temperature for 8 Hour. The resulting white solid (compound a) was filtered off, and the filtrate was stirred for 8 hours (this operation was repeated twice) to obtain a total of 5.50 g of compound a (yield 56%).

(ii) Synthesis of ligand precursor (compound b)

The ligand precursor (compound b) was synthesized by the following reaction procedure.

[chem 45]

To 9.21 g of N-phenylo-phenylenediamine (molecular weight 184.24, 50 mmol) was added 100 ml of toluene, followed by 4.60 g of formic acid (molecular weight 46.03, 100 mmol). Upon stirring at room temperature, a solid formed immediately. Then, it was made to react for 2 hours, refluxing. After the reaction, toluene was distilled off under reduced pressure, and the target product (N-phenylbenzimidazole) was purified by silica gel column chromatography (developing solvent: methylene chloride 95%/methanol 5%, Rf value about 0.2). The recovered amount was 5.60 g (molecular weight 194.24, yield 58%).

To 1.60 g of the obtained N-phenylbenzimidazole (molecular weight 194.24, 8.24 mmol) was added 50 ml of tetrahydrofuran as a solvent, followed by 2.34 g of methyl iodide (molecular weight 141.94, 16.5 mmol), and stirred at room temperature for 8 hours. The resulting white solid (compound b) was filtered off, and the filtrate was stirred for 8 hours (this operation was repeated twice) to obtain a total of 2.22 g of compound b (molecular weight: 336.18, yield: 80%).

(iii) Synthesis of transition metal complex 1

Transition metal complex 1 was synthesized by the following reaction procedure.

[chem 46]

The entire reaction was carried out under argon flow. 0.672g of compound c (molecular weight 671.70, 1.00 mmol) was added 150 ml of 2-ethoxyethanol as a solvent, followed by 0.626 g of sodium ethoxide (molecular weight 68.05, 9.20 mmol), and it was stirred at room temperature for 1 hour. 0.807 g of compound b (molecular weight 336.18, 2.40 mmol) was added thereto, followed by 1.44 g of compound a (molecular weight 598.26, 2.40 mmol), and the reaction was carried out under reflux for 2 hours. From the obtained reaction liquid, 2-ethoxyethanol as a solvent was distilled off by heating under reduced pressure, and after cooling, 100 ml of dichloromethane was added, and the solid content was filtered off. Next, the filtrate was distilled off under reduced pressure, the residue was dissolved in 5 ml of dichloromethane, and then 100 ml of hexane was added to precipitate a solid. The solid was purified by silica gel column chromatography (developing solvent: dichloromethane, Rf value about 0.8). As a result, 0.34 g of Compound 1 was obtained (molecular weight 739.89, yield 23%). The obtained transition metal complex 1 was a mixture of two isomers.

The following (1)-(4) were measured about the obtained compound.

<Various measurement results>

(1) FD-MS (field distortion mass spectrum) measurement: the maximum peak value is 740, consistent with the calculated value (calculated value M ⁺ (molecular ion peak) = 740).

The measurement conditions of the FD-MS measurement (field desorption mass spectrometry) are as follows.

Device: HX110 (manufactured by Japan Electronics Co., Ltd.)

Condition: accelerating voltage 8kV

Scanning range (キヤンレンジ) m/z＝50～1500

Emitter Type Carbon

Emitter current 0mA→2mA/min→40mA (hold for 10 minutes)

(2) ¹ H-NMR (500MHz) spectrum measurement: refer to Figure 1

Device: DRX500 (manufactured by Japan Electronics Co., Ltd.)

Determination solvent: solvent CD ₂ Cl ₂ (deuterated dichloromethane), benchmark 5.32ppm

The structure of Compound 1 was determined from the results of (1) and (2) above.

(3) ¹³ C-NMR (125MHz) Spectrum Measurement: Refer to Table 1

Measurement: DRX500 (manufactured by JEOL Ltd.)

Determination solvent: solvent CD ₂ Cl ₂ (deuterated dichloromethane), benchmark 54.0ppm

A total of 72 peaks were observed in ¹³ C-NMR (see Table 1), which indicates that Compound 1 having 36 carbons with different environments can be obtained as a mixture of two isomers. Among them, a total of 8 peaks were observed from the cross-linking site of the butylene chain, which were divided into four types (52.63ppm, 50.88ppm, 48.56ppm, 48.34ppm) of the α-position of nitrogen and four types of β-position of nitrogen (30.46ppm , 29.96ppm, 27.01ppm, 25.33ppm). In addition, a total of 6 types of carbene carbons were observed, which were classified into carbene carbon species at the imidazol-2-ylidene site (177.42ppm, 175.77ppm, 175.07ppm, 173.22ppm) and benzimidazol-2-ylidene site. Carbene carbon 2 kinds (190.38ppm, 185.84ppm).

[Table 4]

Form 1

no 13C-NMR(ppm) no 13C-NMR(ppm) no 13C-NMR(ppm) no 13C-NMR(ppm) #1 25.33 #19 111.95 #37 122.87 #55 147.02 #2 27.01 #20 112.04 #38 122.96 #56 147.58 #3 29.96 #twenty one 114.41 #39 124.02 #57 148.00 #4 30.46 #twenty two 114.58 #40 124.20 #58 148.08 #5 33.18 #twenty three 116.02 #41 125.02 #59 148.56 #6 33.48 #twenty four 116.36 #42 125.29 #60 148.77 #7 48.34 #25 120.19 #43 125.50 #61 149.76 #8 48.56 #26 120.39 #44 125.52 #62 150.00 #9 50.88 #27 120.45 #45 133.00 #63 150.52 #10 52.63 #28 120.57 #46 133.47 #64 150.67 #11 109.91 #29 120.64 #47 136.76 #65 151.06 #12 110.05 #30 120.82 #48 137.49 #66 152.26 #13 110.77 #31 120.95 #49 137.59 #67 173.22 #14 110.84 #32 121.05 #50 137.79 #68 175.07 #15 111.01 #33 121.09 #51 138.51 #69 175.77 #16 111.20 #34 121.19 #52 138.54 #70 177.42 #17 111.40 #35 122.04 #53 140.18 #71 185.84 #18 111.45 #36 122.04 #54 140.22 #72 190.38

(4) Determination of two-dimensional NMR (C-H COZY and H-H COZY):

Measure the two-dimensional NMR (C-H COZY and H-H COZY) of the butylene chain site, and determine the chemical shift values of the two isomers as follows.

<Isomer 1>

[chem 47]

NMR compound shift value (in ppm)

<Isomer 2>

[chem 48]

NMR compound shift value (in ppm)

The structure of Compound 1 was confirmed from the results of (1) to (4) above.

(5) Measurement of luminescence spectrum (at room temperature): refer to Figure 4

Device: F-4500 Fluorescence Spectrophotometer

Determination solvent: dichloromethane

From FIG. 4 , it can be seen that in a solution state, light is emitted in the ultraviolet region to the cyan region.

Comparative Example 1 (synthesis of comparative compound 1)

(i) Synthesis of ligand (compound d)

The ligand (compound d) was synthesized by the following reaction procedure.

[chem 49]

To 5.00 g of N-phenylimidazole (molecular weight 144.18, 34.7 mmol), and 9.85 g of methyl iodide (molecular weight 141.94, 69.4 mmol), 100 ml of tetrahydrofuran was added, and stirred at room temperature for 8 hours. The resulting white solid (compound d) was filtered off, and the filtrate was stirred for 8 hours (this operation was repeated twice) to obtain a total of 9.93 g of compound d (molecular weight: 286.12, yield: 95%).

(ii) Comparative synthesis of compound 1

Comparative compound 1 was synthesized by the following reaction procedure.

[chemical 50]

The entire reaction was carried out under argon flow. 50 ml of 2-ethoxyethanol was added as a solvent to 0.672 g of compound c (molecular weight 671.70, 1.00 mmol), followed by 0.626 g of sodium ethoxide (molecular weight 68.05, 9.20 mmol), and stirred at room temperature for 1 hour. 2.06 g of compound d (molecular weight: 286.11, 7.20 mmol) was added thereto, and reacted under reflux for 2 hours. From the obtained reaction liquid, 2-ethoxyethanol as a solvent was distilled off by heating under reduced pressure, and after cooling, 100 ml of dichloromethane was added, and then the solid content was filtered out. Next, the filtrate was distilled off under reduced pressure, the residue was dissolved in 5 ml of dichloromethane, and then 100 ml of hexane was added to precipitate a solid. The solid was purified by silica gel column chromatography (developing solvent: dichloromethane, Rf value about 0.8). As a result, 0.850 g of Comparative Compound 1 was obtained (molecular weight 663.79, yield 64%). The obtained comparative compound 1 was a mixture of two isomers (facial body and meridional body).

Facial body: In a transition metal coordination compound composed of a regular octahedral structure, when there are three equivalent ligands, the ligands form a 90-degree angle with each other and are located on the same side.

Meridional body: In a transition metal coordination compound composed of a regular octahedral structure, two of the three equivalent ligands form a 180-degree angle with each other.

The following (1)-(3) was measured about the obtained compound under the same conditions as Example 1.

<Various measurement results>

(1) FD-MS measurement: the maximum peak is 644, consistent with the calculated value (calculated value M ⁺ (molecular ion peak) = 644).

(2) ¹ H-NMR (500MHz) spectrum measurement: refer to Figure 2

The structure of Comparative Compound 1 was confirmed from the results of (1) and (2) above.

(3) Measurement of luminescence spectrum (at room temperature): refer to Figure 4

Comparative example 2 (synthesis of comparative compound 2)

Comparative compound 2 was synthesized by the following reaction procedure.

[Chemical 51]

The entire reaction was carried out under argon flow. 50 ml of 2-ethoxyethanol was added as a solvent to 0.302 g of compound c (molecular weight 671.70, 0.45 mmol), followed by 0.306 g of sodium ethoxide (molecular weight 68.05, 4.50 mmol), and stirred at room temperature for 1 hour. 1.08 g of compound b (molecular weight: 300.14, 3.60 mmol) was added thereto, and reacted under reflux for 2 hours. The solid content was filtered out from the obtained reaction solution, and the solid content was washed sufficiently with 2-ethoxyethanol, ethanol, and hexane to obtain 0.45 g of the target comparative compound 2 (molecular weight: 813.97, yield: 61%). The obtained comparative compound 2 was a facial body.

The following (1)-(3) was measured about the obtained compound under the same conditions as Example 1.

<Various measurement results>

(1) FD-MS measurement: the maximum peak is 814, consistent with the calculated value (calculated value M ⁺ (molecular ion peak) = 814).

(2) ¹ H-NMR (500MHz) spectrum measurement: refer to Figure 3

The structure of Comparative Compound 2 was determined from the results of (1) and (2) above.

(3) Measurement of luminescence spectrum (at room temperature): refer to Figure 4

Embodiment 2 (synthesis of transition metal coordination compound 2)

(i) Synthesis of the crosslinking group site (compound e)

Synthesize 1.25 g of the following compound e ( Molecular weight 336.89, 3.71 mmol).

[Chemical 52]

(ii) Synthesis of ligand (compound f)

The ligand (compound f) was synthesized by the following reaction procedure.

[Chemical 53]

Add 40ml tetrahydrofuran to 1.93g N-phenylimidazole (molecular weight 144.18, 13.4 mmol), and 1.25g compound e (molecular weight 336.89, 3.71 mmol), and reflux for 8 hours. The resulting white solid was filtered off to obtain 1.19 g of compound f (molecular weight 769.41, 1.54 mmol, yield 32%).

(ii) Synthesis of transition metal complex 2

Transition metal complex 2 was synthesized by the following reaction procedure.

[Chemical 54]

The entire reaction was carried out under argon flow. 30 ml of 2-ethoxyethanol was added as a solvent to 0.517 g of compound c (molecular weight 671.70, 0.77 mmol), followed by 0.419 g of sodium ethoxide (molecular weight 68.05, 6.16 mmol), and stirred at room temperature for 1 hour. 1.19 g of compound f (molecular weight: 769.41, 1.54 mmol) was added thereto, and reacted under reflux for 2 hours. From the obtained reaction liquid, 2-ethoxyethanol as a solvent was distilled off by heating under reduced pressure, and after cooling, 60 ml of dichloromethane was added, and the solid content was filtered off. Next, the filtrate was distilled off under reduced pressure, the residue was dissolved in 10 ml of dichloromethane, and then 50 ml of hexane was added to precipitate a solid. The solid was purified by silica gel column chromatography (developing solvent: dichloromethane, Rf value about 0.8). As a result, 0.069 g of compound 2 (molecular weight 715.87, 0.096 mmol, yield 5%) was obtained.

As a result of FD-MS measurement of the obtained compound 2, the maximum peak was 716, which was consistent with the calculated value (calculated value M ⁺ (molecular ion peak) = 716). In addition, as a result of the luminescence spectrum at room temperature, the maximum luminescence peak wavelengths (λmax) were 388 nm and 407 nm.

Embodiment 3 (synthesis of transition metal coordination compound 3)

The transition metal complex 3 was synthesized by the following reaction procedure.

[Chemical 55]

The entire reaction was carried out under argon flow. 21 ml of 2-ethoxyethanol was added as a solvent to 0.140 g of compound c (molecular weight 671.70, 0.209 mmol), followed by 0.142 g of sodium ethoxide (molecular weight 68.05, 2.09 mmol), and stirred at room temperature for 1 hour. 0.157 g of compound g (molecular weight 376.19, 0.418 mmol) was added thereto, followed by 0.250 g of compound a (molecular weight of 598.26, 0.418 mmol), and the reaction was carried out under reflux for 2 hours. From the obtained reaction solution, 2-ethoxyethanol as a solvent was distilled off by heating under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: dichloromethane, Rf value about 0.8). As a result, 0.013 g of compound 3 (molecular weight 779.91, yield 4%) was obtained.

As a result of FD-MS measurement of the obtained compound 3, the maximum peak value was 780, which was consistent with the calculated value (M ⁺ ) (calculated value M ⁺ =780). In addition, as a result of measuring the luminescence spectrum at room temperature, the maximum luminescence peak wavelength was 449 nm. The obtained transition metal complex 3 was a mixture of two isomers (facial and meridional).

From the above measurement results, it is clear that the emission wavelength can be increased by linking (crosslinking) the ligands of the coordination compound. This phenomenon is useful as a technique capable of adjusting the emission wavelength to a desired value, and is particularly useful for directing a material having an emission wavelength in the ultraviolet region to a material having an emission wavelength in the cyan region. By utilizing this technology, it is possible to provide a material for an organic electroluminescent element that has excellent luminous efficiency and emits blue light.

Industrial availability

As described above in detail, the organic EL device using the transition metal complex of the present invention is extremely useful as a material for an organic EL device that requires high luminous efficiency, long luminous life, and cyan light emission. In addition, the transition metal complex of the present invention is a compound converted to a material emitting light in the cyan region by converting the molecular skeleton of a conventional material having a light emitting wavelength in the ultraviolet region.

Claims (23)

1. A transition metal coordination compound, wherein, The transition metal complex has a ligand having a tridentate or more coordinating teeth formed by a combination of covalent bonds and/or coordinate bonds. 2. A transition metal coordination compound, wherein, The transition metal complex has a ligand having a tetradentate or more coordinating teeth formed by a combination of covalent bonds and/or coordinate bonds. 3. transition metal coordination compound according to claim 1 or 2, wherein, The transition metal coordination compound has a metal carbene bond. 4. transition metal coordination compound according to claim 3, wherein, The metal of the transition metal coordination compound is iridium. 5. A transition metal coordination compound with a metal carbene bond, wherein, The transition metal coordination compound is represented by the following general formula (1), [chemical 1]

In the general formula (1), the bond shown by the solid line (-) represents a covalent bond, the bond represented by an arrow (→) represents a coordination bond, and at least one of L ² →M and L ⁴ →M represents a metallocarbene bond, M represents the metal atom of iridium (Ir) or platinum (Pt), L ¹ -L ² and L ³ -L ⁴ represent cross-linked bidentate ligands, L ⁵ and L ⁶ independently represent monodentate coordination or L ⁵ and L ⁶ cross-linked bidentate ligands (L ⁵ -L ⁶ ), L ¹ and L ³ , L ¹ and L ⁴ , L ² and L ³ , L ² and L ⁴ , L ¹ and L ⁵ , L ¹ and L ⁶ , L ² and L ⁵ , L ² and L ⁶ , L ³ and ^{L 5} , L 3 and L ⁶ , L ⁴ and L ⁵ and L ⁴ and L ⁶ at least A kind of crosslinking through the crosslinking group -Z ¹ -, wherein Z ¹ is from aromatic hydrocarbon, heterocyclic group, chain alkane, chain olefin, and their carbon atoms replaced by silicon atom, nitrogen atom, sulfur atom, A compound selected from compounds substituted with any one of an oxygen atom, a phosphorus atom, and a boron atom, or a divalent residue formed by a combination thereof may also have a substituent, In the case of multiple crosslinking groups -Z ¹ -, they may be the same or different, i represents an integer from 0 to 1, 2+i represents the atomic valence of the metal M, j represents an integer from 0 to 4, when i and when j is plural, each of ^L5 and ^L6 may be the same or different, and adjacent groups may also be crosslinked; ^L1 and ^L3 each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, a divalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent, or A divalent carboxyl-containing group having 1 to 30 carbon atoms that has a substituent, a divalent amino or hydroxyl-containing hydrocarbon group that may also have a substituent, and a ring substituent having 3 to 50 ring carbon atoms that may also have a substituent Alkyl group, an optionally substituted C1-30 alkylene group, an optionally substituted C2-30 alkenylene group, an optionally substituted C7-40 aralkylene group base; L ² and L ⁴ each independently represent a monovalent group having carbene carbon which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may also have a substituent, or a monovalent aromatic hydrocarbon group which may have a substituent A monovalent heterocyclic group with 3 to 30 ring atoms, at least one of ^L2 and ^L4 is a monovalent group with carbene carbon that may also have a substituent; ^L5 is a monovalent aromatic hydrocarbon group with 6 to 30 ring carbon atoms that may have a substituent, a monovalent heterocyclic group with 3 to 30 ring atoms that may have a substituent, or a carbon number that may have a substituent A monovalent carboxyl group of 1 to 30, a monovalent hydrocarbon group containing an amino group or a hydroxyl group that may have a substituent, a cycloalkyl group with 3 to 50 ring carbon atoms that may have a substituent, and a carbon number that may have a substituent An alkyl group of 1 to 30, an alkenyl group of 2 to 30 carbons which may also have a substituent, an aralkyl group of 7 to 40 carbons which may also have a substituent, and when ^L5 and ^L6 are crosslinked is the divalent group of each group; ^L6 is a heterocyclic ring with 3 to 30 ring carbon atoms which may also have a substituent, a carboxylic acid ester with 1 to 30 carbon atoms or a carboxylic acid amide with 1 to 30 carbon atoms which may also have a substituent, and may also have a substituent Amines with substituents, phosphines with substituents, isocyanides with substituents, ethers with 1 to 30 carbon atoms with substituents, thioethers with 1 to 30 carbon atoms with substituents, Or a double bond-containing compound having 1 to 30 carbon atoms that may have a substituent, and when L ⁵ and L ⁶ are crosslinked, it is a monovalent group of each of the above-mentioned compounds. 6. the transition metal coordination compound with metal carbene bond according to claim 5, wherein, The transition metal coordination compound is represented by the following general formula (2), [Chem 2]

In the general formula (2), the bond shown by the solid line represents a covalent bond, the bond represented by an arrow represents a coordination bond, and at least one of L ² →M and L ⁴ →M represents a metal carbene bond; M, L ¹ ~L ⁶ are the same as above; L ¹ -L ² and L ³ -L ⁴ represent cross-linked bidentate ligands, L ⁵ and L ⁶ independently represent monodentate ligands or L ⁵ and L ⁶ carry out Cross-linked bidentate ligands (L ⁵ -L ⁶ ), L ¹ and L ³ , L ¹ and L ⁴ , L 2 and L ³ , L ² and L ⁴ , ^{L 1 and} L ⁵ , L At least one ^{of 1} and L ⁶ , L ² and L ⁵ , L ² and L ⁶ , L ³ and L ⁵ , L ³ and L ⁶ , L ⁴ and L ^{5 , and L 4 and} L ⁶ passes through the crosslinking group -Z ¹ - performing crosslinking, wherein Z ¹ is the same as described above; n represents an integer from 0 to 1, and 2+n represents the atomic valence of the metal M. 7. the transition metal coordination compound with metal carbene bond according to claim 5, wherein, (L ¹ -L ² )M and/or (L ³ -L ⁴ )M is a structure represented by the following general formula (3), [Chem 3]

In the general formula (3), C (carbon atom) → M represents a metal carbon olefin bond, M represents a metal atom of Ir or Pt, X is a nitrogen-containing group (-NR ¹ -), a phosphorus-containing group (-PR ¹ -), oxygen (-O-) or sulfur (-S-), Y is nitrogen-containing group (-NR ¹ R ² ), phosphorus-containing group (-PR ¹ ), oxygen-containing group (-OR ¹ ) or a sulfur-containing group (-SR ¹ ), X and Y can also be cross-linked to form a ring structure, Wherein, R ¹ and R ² each independently represent 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 also have a substituent, or an alkyl group which may have a substituent An aromatic hydrocarbon group with 6 to 30 ring carbon atoms, a cycloalkyl group with 3 to 50 ring carbon atoms that may have a substituent, an aralkyl group with 7 to 40 carbon atoms that may also have a substituent, or a substituted An alkenyl group having 2 to 30 carbon atoms, a heterocyclic group having 3 to 30 ring atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may also have a substituent, or an alkoxy group having 1 to 30 carbon atoms which may also have a substituent An aryloxy group with 6 to 30 ring carbon atoms, an alkylamino group with 3 to 30 carbon atoms that may also have substituents, an arylamino group with 6 to 30 carbon atoms that may also have substituents, or an arylamino group that may also have substituents An alkylsilyl group with 3 to 30 carbons, an arylsilyl group with 6 to 30 carbons that may also have a substituent, a carboxyl-containing group that may also have a substituent with 1 to 30 carbons, ^R1 and ^R2 can also be cross-linked; Z is an atom forming a covalent bond with the metal M, and is a carbon, silicon, nitrogen or phosphorus atom, and the A ring containing Z is an aromatic hydrocarbon group with 3 to 40 ring carbon atoms that may also have a substituent or may also have a substitution An aromatic heterocyclic group having 3 to 40 ring atoms. 8. the transition metal coordination compound with metal carbene bond according to claim 5, wherein, Said M is Ir. 9. the transition metal coordination compound with metal carbene bond according to claim 5, wherein, The transition metal coordination compound is represented by the following general formula (4), [chemical 4]

In the general formula (4), C (carbon atom) → M represents a metal carbene bond, M represents a metal atom of Ir or Pt, K represents an integer of 1 to 3, m represents an integer of 0 to 2, and k+m represents a metal Atomic valence of M, K+m [chemical 5]

(Substituted) N-phenyl-N'-R ³ -imidazol-2-ylidene-C ² , C ² ' groups and [chemical 6]

(Substituted) 2-phenylpyridine-N, at least two of the C ² ' groups are cross-linked via the cross-linking group -Z ¹ -, wherein Z ¹ is the same as described above; ^R3 is an alkyl group with 1 to 30 carbon atoms that may also have a substituent, a halogenated alkyl group with 1 to 30 carbon atoms that may also have a substituent, or an aromatic hydrocarbon group with 6 to 30 ring carbon atoms that may also have a substituent , a cycloalkyl group with 3 to 30 ring carbon atoms that may also have a substituent, an aralkyl group with a carbon number of 7 to 40 that may also have a substituent, and an alkenyl group with 2 to 30 carbon atoms that may also have a substituent , a heterocyclic group with 3 to 30 ring atoms that may also have substituents, an alkylsilyl group with 3 to 30 ring atoms that may also have substituents, an aromatic group with 6 to 30 carbon atoms that may also have substituents A silyl group, a group containing a carboxyl group with 1 to 30 carbons; R ⁴ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom, a thiocyano group or a cyano group, a nitro group, a -S(=O) ₂ R ¹ group or a -S(=O)R ¹ group, wherein R ¹ and the Similarly, an alkyl group having 1 to 30 carbon atoms which may also have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may also have a substituent, an aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may also have a substituent, A cycloalkyl group having 3 to 30 ring carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may also have a substituent, an alkenyl group having 2 to 30 carbon atoms which may also have a substituent, A heterocyclic group having 3 to 30 ring atoms which may also have a substituent, an alkoxy group having 1 to 30 carbon atoms which may also have a substituent, an aryloxy group having 6 to 30 ring carbon atoms which may also have a substituent , an alkylamino group having 3 to 30 ring atoms which may also have a substituent, an alkylsilyl group having 3 to 30 ring atoms which may also have a substituent, an aryl group having 6 to 30 carbon atoms which may also have a substituent A silyl group, a carboxyl group-containing group having 1 to 30 carbon atoms, and R ⁴ to R ¹⁷ may be crosslinked between adjacent groups. 10. the transition metal coordination compound with metal carbene bond according to claim 9, wherein, Said M is Ir, and the transition metal coordination compound is represented by the following general formula (5), [chemical 7] In the general formula (5), C (carbon atom)→Ir represents a metal carbene bond; K, m, and R ³ to R ¹⁷ are the same as described above; K+m (substituted) N-phenyl-N' At least two of -R ³ -imidazol-2-ylidene-C ² , C ² ' group and (substituted) 2-phenylpyridine-N, C ² ' group are cross-linked via the cross-linking group -Z ¹ - , where Z ¹ is the same as described. 11. A transition metal coordination compound, wherein, The transition metal coordination compound is represented by the following general formula (6), [chemical 8] In general formula (6), A represents the cross-linked bidentate ligand group formed by L ¹¹ -(Z ¹¹ ) _d -L ¹² , and B represents the cross-linked group formed by L ¹³ -(Z ¹² ) _e -L ¹⁴ The bidentate ligand group, in addition, C represents the cross-linked bidentate ligand group formed by L ¹⁵ -(Z ¹³ ) _f -L ¹⁶ , L ¹¹ -, L ¹³ - and L ¹⁵ - respectively represent the Ir( Iridium) covalent bond (L ¹¹ -Ir, L ¹³ -Ir and L ¹⁵ -Ir), L ¹² →, L ¹⁴ → and L ¹⁶ → respectively represent the coordination bond with Ir (iridium) (L ¹² →Ir , L ¹⁴ →Ir and L ¹⁶ →Ir); ^X1 is a cross-linking group formed by an acyclic structure with an atomic number of 1 to 18, and is a crosslinking group selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom. The trivalent residue of the compound composed of atoms may also have a substituent; Y ¹ represents the cross-linking group that combines X and A, Y ² represents the cross-linking group that combines X and B, Y ³ represents the cross-linking group that combines X and C, Y ¹ is combined with L ¹¹ , L ¹² or Z ¹¹ , Y ² binds to L ¹³ , L ¹⁴ or Z ¹² , Y ³ binds to L ¹⁵ , L ¹⁶ or Z ¹³ . Y ¹ , Y ² and Y ³ each independently represent a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, It may also have a substituent. a, b, and c each independently represent an integer of 0 to 10, and when a, b, or c is a plural number, a plurality of Y ¹ , Y ^{2 ,} or Y ³ may be the same or different. Z ¹¹ represents the cross-linking group combining L ¹¹ and L ¹² , Z ¹² represents the cross-linking group combining L ¹³ and L ¹⁴ , Z ¹³ represents the cross-linking group combining L ¹⁵ and L 16, ^{Z 11 ,} Z ¹² and Z ¹³ Each independently represents a divalent residue of a compound composed of an atom selected from a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom, and may have a substituent, when Z When ¹¹ is directly combined with ^Y1 , when ^Z12 is directly combined with ^Y2 , or when ^Z13 is directly combined with ^Y3 , ^Z11 , ^Z12 and ^Z13 become the corresponding trivalent groups respectively, d, e and f each independently represents an integer from 0 to 10, and when d, e or f is a complex number, a plurality of Z ¹¹ , Z ¹² or Z ¹³ may be the same or different; L ¹¹ , L ¹³ and L ¹⁵ each independently represent a divalent aromatic hydrocarbon group having 6 to 30 ring carbon atoms which may have a substituent, or a divalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent , a divalent carboxyl-containing group with 1 to 30 carbon atoms that may also have a substituent, a divalent amino or hydroxyl-containing hydrocarbon group that may also have a substituent, or a ring with 3 to 50 carbon atoms that may also have a substituent cycloalkylene group, an alkylene group with 1 to 30 carbon atoms that may have a substituent, an alkenylene group with 2 to 30 carbon atoms that may also have a substituent, and an alkenylene group with 7 to 40 carbon atoms that may also have a substituent Aralkylene, when L ¹¹ is directly combined with Y ¹ , when L ¹³ is directly combined with Y ² , or when L ¹⁵ is directly combined with Y ³ , L ¹¹ , L ¹³ and L ¹⁵ become the corresponding trivalent group; L ¹² , L ¹⁴ and L ¹⁶ each independently represent a monovalent group having carbene carbon which may also have a substituent, or a monovalent heterocyclic group having 3 to 30 ring atoms which may also have a substituent, when L When ¹² is directly bonded to ^Y1 , when ^L14 is directly bonded to ^Y2 , or when ^L16 is directly bonded to ^Y3 , ^L12 , ^L14 , and ^L16 become corresponding divalent groups, respectively. 12. transition metal coordination compound according to claim 11, wherein, The crosslinking group X has any one of the following structures, [chemical 9]

Wherein, R is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may also have a substituent, a halogenated alkyl group having 1 to 30 carbon atoms which may also have a substituent, or a ring carbon atom group having 6 to 30 carbon atoms which may also have a substituent aromatic hydrocarbon group, a cycloalkyl group with 3 to 50 ring carbon atoms that may also have a substituent, an aralkyl group with a carbon number of 7 to 40 that may also have a substituent, and an aralkyl group with 2 to 30 carbon atoms that may also have a substituent alkenyl, a heterocyclic group with 3 to 30 ring atoms that may also have a substituent, an alkoxy group with 1 to 30 carbon atoms that may also have a substituent, and a ring carbon group with 6 to 30 carbon atoms that may also have a substituent Aryloxy group having 30 carbon atoms, alkylamino group having 3 to 30 carbon atoms which may have a substituent, arylamino group having 6 to 30 carbon atoms which may also have a substituent, alkyl group having 3 to 30 carbon atoms which may also have a substituent A silyl group, an arylsilyl group having 6 to 30 carbon atoms which may have a substituent, or a carboxyl group-containing group having 1 to 30 carbon atoms may have a substituent. 13. transition metal coordination compound according to claim 11, wherein, The crosslinking group X has any one of the following structures, [chemical 10]

Wherein, R is the same as described. 14. transition metal coordination compound according to claim 11, wherein, The crosslinking group X has the following structure, [chemical 11]

Wherein, R is the same as described. 15. transition metal coordination compound according to claim 11, wherein, The sum of the atomic weights constituting the following crosslinking sites (7) in the general formula (6) is 200 or less, [chemical 12]

16. transition metal coordination compound according to claim 15, wherein, The sum of the atomic weights constituting the crosslinking site (7) is 100 or less. 17. An organic electroluminescence element, the organic electroluminescence element holds between the anode and the cathode an organic thin film layer having at least a light-emitting layer consisting of one or more layers, wherein, At least one of the organic thin film layers contains the transition metal complex according to claim 1, 2, 5 or 11. 18. The organic electroluminescence element according to claim 17, wherein, The light-emitting layer contains the transition metal complex according to claim 1, 2, 5 or 11 as a light-emitting material. 19. The organic electroluminescence element according to claim 17, wherein, The light emitting layer contains the transition metal complex according to claim 1, 2, 5 or 11 as a dopant. 20. The organic electroluminescence element according to claim 17, wherein, An electron injection layer and/or an electron transport layer is provided between the light-emitting layer and the cathode, and the electron injection layer and/or electron transport layer contains a π-electron-deficient nitrogen-containing heterocyclic derivative as a main component. 21. The organic electroluminescence element according to claim 17, wherein, A reducing dopant is added to the interface region between the cathode and the organic thin film layer. 22. The organic electroluminescence element according to claim 17, wherein, The transition metal coordination compound is the transition metal coordination compound represented by the general formula (4) described in claim 9 . 23. The organic electroluminescence element according to claim 17, wherein, The transition metal coordination compound is the transition metal coordination compound represented by the general formula (5) described in claim 10 .

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