Metal complex, and light-emitting material and photocatalyst each comprising said metal complex

Abstract

The present invention provides a metal complex which exhibits strong light emission in the visible light region (particularly, in the blue region) and which has a strong oxidizing power when the complex is in an excited state. Provided is an iridium complex represented by general formula (1). (In general formula (1), M represents an iridium atom or a platinum atom, N represents a nitrogen atom, C represents a carbon atom, F represents a fluorine atom. Ra and Rb each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. At least one of Ra and Rb is a halogen atom. R1 to R4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. R2 and R3 may be bonded to each other to form a ring structure. m represents 1 or 2. m is 2 when M is an iridium atom, and m is 1 when M is a platinum atom. X- represents a counter anion. L represents a neutral bidentate ligand which is capable of forming two M-nitrogen bonds.)

Description

Metal complex, luminescent material and photocatalyst made from said metal complex

[0001] The present invention relates to a novel metal complex useful as a material for organic electroluminescent devices and as a photocatalyst.

[0002] Organic electroluminescent devices are increasingly being used in television and mobile phone displays, and further improvements in luminous efficiency are strongly desired in order to reduce power consumption. Light-emitting materials used in organic electroluminescent devices can be broadly classified into fluorescent materials, which utilize light emission from an excited singlet state, and phosphorescent materials, which utilize light emission from an excited triplet state. The use of phosphorescent materials as luminescent materials theoretically increases luminous efficiency by four times compared to conventional fluorescent materials, and thus phosphorescent materials have been actively developed to date. However, of the three primary luminescent materials (blue, green, and red) required for full-color display, no phosphorescent material has been adopted for the blue color. This is because conventionally known blue phosphorescent materials still have many technical challenges, such as the color purity and durability of their emitted light, which are necessary for practical use.

[0003] For example, a cyclometallated iridium complex (formula (A)) having a fluorine-substituted phenylpyridine ligand is widely known as a blue phosphorescent material, but its maximum emission wavelength λmax is 470 nm (see Patent Document 1), and in order to achieve pure blue emission, it is necessary to shift the emission spectrum to shorter wavelengths.

[0004] <Formula (A)>

[0005] On the other hand, cyclometallated iridium complexes bearing phenylpyridine-based ligands are widely known to possess a long-lived, high-energy lowest triplet excited state (T1) and function as photocatalysts driving organic molecule transformation reactions (see Non-Patent Document 1). In the field of organic chemistry, the development of photocatalysts with strong oxidizing power in their excited states is an important research topic. This is because petroleum, the raw material for the organic chemical industry, is reduced underground over many years and is composed mostly of carbon and hydrogen. Oxidation reactions are required to produce useful chemicals from petroleum. To date, cyclometallated iridium complexes (formula (B)) bearing 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine and 4,4'-di-tert-butyl-2,2'-bipyridine have been used as photocatalysts (see Non-Patent Document 2). However, their oxidizing power is still insufficient, and there is a strong demand for photocatalysts with even stronger oxidizing power in their excited states.

[0006] <Formula (B)>

[0007] JP 2002-117978

[0008] Chem. Rev., 2013, Vol. 113, p. 5322 Chem. Mater., 2005, Vol. 17, p. 5712

[0009] An object of the present invention is to provide a novel metal complex which exhibits strong luminescence in the visible light region (particularly in the blue region) and has strong oxidizing power in an excited state.

[0010] In view of the above circumstances, the present inventors have synthesized numerous metal complexes and conducted extensive research to gain knowledge about the luminescence properties and electrochemical properties (redox potential) of platinum group metal complexes. As a result, they have discovered that a novel metal complex having a specific structure represented by general formula (1) not only emits light with high efficiency in the visible light region (particularly the blue region) but also has strong oxidizing power in the excited state, leading to the completion of the present invention. This is an important and new finding obtained by the present inventors through numerous and meticulous experiments.

[0011] That is, the present invention provides the following.

[0012] (1) A metal complex represented by the following general formula (1): (In general formula (1), M represents an iridium atom or a platinum atom, N represents a nitrogen atom, C represents a carbon atom, and F represents a fluorine atom. R a and R b each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. a and R b At least one of R is a halogen atom. 1 ~R 4 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. 2 and R 3 may be bonded to each other to form a ring structure. m represents 1 or 2. However, when M is an iridium atom, m is 2, and when M is a platinum atom, m is 1. X - represents a counter anion. L represents a neutral bidentate ligand capable of forming two M-nitrogen bonds. (2) R a and R b (3) The metal complex according to (1) above, wherein at least one of R a and R bis a fluorine atom. (4) The metal complex according to (1) above, characterized in that L is 2,2'-bipyridine which may have a substituent. (5) The metal complex according to (4) above, characterized in that 2,2'-bipyridine has one or more substituents selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group. (6) The metal complex according to (1) above, characterized in that M is an iridium atom. (7) A luminescent material comprising the metal complex according to any one of (1) to (6) above. (8) A photocatalyst comprising the metal complex according to any one of (1) to (6) above. (9) A metal complex represented by the following general formula (2): General formula (2) (In general formula (2), M represents an iridium atom or a platinum atom, N represents a nitrogen atom, C represents a carbon atom, and F represents a fluorine atom. Y represents a halogen atom. R a and R b each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. a and R b At least one of R is a halogen atom. 1 ~R 4 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. 2 and R 3may be bonded to each other to form a ring structure. m represents 1 or 2. However, when M is an iridium atom, m is 2, and when M is a platinum atom, m is 1.

[0013] The novel metal complex of the present invention exhibits high-efficiency, high-brightness emission in the visible light region (particularly the blue region), and therefore, light-emitting devices using the compound are suitable for displays, backlights, illumination light sources, etc. Furthermore, since the novel metal complex of the present invention has strong oxidizing power in the excited state, it can be suitably used as a photocatalyst for, for example, pharmaceutical synthesis or labeling of biomolecules.

[0014] FIG. 1 is a diagram showing the emission spectrum (in 2-MeTHF) of Compound 1 of the present invention at 77 K.

[0015] The present invention will now be described in detail with reference to the following embodiments, but the present invention is not limited to these descriptions. Various modifications may be made to the embodiments as long as the effects of the present invention are achieved.

[0016] The metal complex of the present invention transitions from the ground state to an excited state upon absorbing light. The excited metal complex then emits light in the visible light region as a light-emitting material, or acts as a photocatalyst to cause electron or energy transfer between the metal complex and a reaction substrate, thereby promoting an organic molecule conversion reaction.

[0017] The photocatalyst of the present invention is also called a photoredox catalyst, photoredox catalyst, visible light redox catalyst, visible light redox photocatalyst, photoredox sensitizer, photosensitizer, or photooxidation-reduction catalyst.

[0018] In the description of the general formula of the present invention, hydrogen atoms include isotopes (such as deuterium atoms), and atoms constituting substituents also include their isotopes.

[0019] First, the symbols (M, N, C, F, X) described in the general formula (1) and the general formula (2) - , Y, m, R a , R b , R 1 ~R 4 , L) will be explained below.

[0020] M represents an iridium atom or a platinum atom, and preferably an iridium atom.

[0021] N represents a nitrogen atom.

[0022] C represents a carbon atom.

[0023] F represents a fluorine atom.

[0024] X - represents a counter anion, which plays a role in neutralizing the charge. There are no particular limitations on the counter anion, as long as it is one that is commonly used. For example, a halogen ion (Cl - ,Br - , I - ), SO4 2- , SbF6 - , PF6 - , BF4 - , B(C6F5)4 - , ClO - , CF3CO2 - , CF3SO3 - , p-toluenesulfonate ion, ethyl sulfate ion, tetracyanoborate anion, tris(halogenoalkylsulfonyl)methide anion (e.g., (CF3SO2)3C - ), di(halogenoalkylsulfonyl)imide anions (e.g., (CF3SO2)2N - ), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion (BArF - ) and others. Among them, CF3CO2 - , halogen ions or PF6 - is preferred, and PF6 - is more preferred.

[0025] Y represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0026] m represents 1 or 2. However, when M is an iridium atom, m is 2, and when M is a platinum atom, m is 1.

[0027] R a and R beach independently represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. a and R b At least one of R is a halogen atom. a and R b Among them, R b is preferably a halogen atom, and R a and R b It is more preferable that R is simultaneously a halogen atom. a and R b The halogen atom used in R is preferably a fluorine atom or a bromine atom, and more preferably a fluorine atom. a and R b Among them, R b is preferably a fluorine atom, and R a and R b It is particularly preferred that simultaneously be a fluorine atom.

[0028] R 1 ~R 4 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted heterocyclic oxy group, an optionally substituted heterocyclic thio group, an optionally substituted carboxy group, an acyl group, an acyloxy group, an optionally substituted amide group, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group.

[0029] Among these, a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group which may have a substituent, a halogen atom, or a trifluoromethyl group is preferred.

[0030] Among the above preferred ranges, R 1 , R3 , and R 4 is particularly preferably a hydrogen atom or an alkyl group which may have a substituent, and most preferably a hydrogen atom.

[0031] Among the above preferred ranges, R 2 is particularly preferably a hydrogen atom, an alkyl group which may have a substituent, or a carboxy group which may have a substituent.

[0032] R 1 ~R 4 Examples of the substituents in the various groups which may have the above-mentioned substituents in R 1 ~R 4 Examples of the alkyl group include the various groups described above with respect to (i.e., an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted heterocyclic oxy group, an optionally substituted heterocyclic thio group, an optionally substituted carboxy group, an acyl group, an acyloxy group, an optionally substituted amide group, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group).

[0033] R 2 and R 3 may be bonded to each other to form a ring structure (which may be either a saturated ring or an unsaturated ring, and which may further be substituted with the above-mentioned substituents).

[0034] L represents a neutral bidentate ligand capable of forming two M-nitrogen bonds. It is preferable that the neutral bidentate ligand has two pyridine rings, and that the nitrogen atoms on the pyridine rings and M form an M-nitrogen bond. The neutral bidentate ligand may have a substituent, and adjacent substituents may be bonded to form a ring structure (which may be either a saturated ring or an unsaturated ring, and may be further substituted with the above-mentioned substituents).

[0035] Examples of such neutral bidentate ligands include 2,2'-bipyridine, which may have a substituent, represented by the following general formula (3), 1,10-phenanthroline, which may have a substituent, represented by the following general formula (4), 2,2'-dipyridylamine, which may have a substituent, represented by the following general formula (5), and 2,2'-dipyridylmethane, which may have a substituent, represented by the following general formula (6). Among these, 2,2'-bipyridine, which may have a substituent, represented by the following general formula (3), or 1,10-phenanthroline, which may have a substituent, represented by the following general formula (4) is preferred, and 2,2'-bipyridine, which may have a substituent, represented by the following general formula (3) is more preferred. In the following general formulas (3) to (6), * represents the bonding site with M.

[0036] General formula (3)

[0037] General formula (4)

[0038] General formula (5)

[0039] General formula (6)

[0040] In general formulas (3) to (6), R 5 ~R 17are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. Adjacent substituents may be bonded to each other to form a ring structure (which may be either a saturated ring or an unsaturated ring, and may further be substituted with the aforementioned substituents).

[0041] Among these, a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group is preferred, and a hydrogen atom, an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group is more preferred.

[0042] R 5 , R 8 , R 9 , and R 12 is particularly preferably a hydrogen atom.

[0043] R 6 , R 7 , R 10 , R 11 , R 13 , and R 14 It is particularly preferable that R is a hydrogen atom, an alkyl group which may have a substituent, a carboxy group which may have a substituent, or a trifluoromethyl group. 6 , R 7 , R 10 , R 11, R 13 , and R 14 The alkyl group used in the above, which may have a substituent, is preferably a trialkylammonium alkyl group, a carboxyalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an amido alkyl group, a carboalkoxyalkyl group, an aminoalkyl group, or an alkoxycarbonylalkyl group, which will be described later.

[0044] R 15 , R 16 , and R 17 It is more particularly preferable that the group is a hydrogen atom or an alkyl group which may have a substituent.

[0045] In general formula (3), R 5 ~R 12 It is preferable that at least one of them is selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group.

[0046] In general formula (4), R 5 ~R 7 , and R 10 ~R 14 It is preferable that at least one of them is selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group.

[0047] In general formula (5), R 5 ~R 12 , and R 15 It is preferable that at least one of them is selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group.

[0048] In general formula (6), R 5 ~R 12 , R 16 , and R 17It is preferable that at least one of them is selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group.

[0049] R 5 ~R 17 Examples of the substituents in the various groups which may have the above-mentioned substituents in R 5 ~R 17 Examples of the alkyl group include the various groups described above with respect to (i.e., an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted amino group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted heterocyclic oxy group, an optionally substituted heterocyclic thio group, an optionally substituted carboxy group, an acyl group, an acyloxy group, an optionally substituted amide group, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group).

[0050] Unless otherwise specified in each description in this specification, the "alkyl group" may be straight-chain, branched or cyclic, and may have a substituent.

[0051] Examples of the alkyl group which may have a substituent (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group, a lauryl group, a fluorine-substituted alkyl group (for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, etc.), a cyano-substituted alkyl group (for example, a 4-cyanobutyl group, a 3-cyanobutyl group, a 2-cyanobutyl group, a 5-cyanopentyl group, a 4-cyanopentyl group, a 3-cyanopentyl group, a 2-cyanopentyl group, etc.), a trialkylammonium alkyl group (a trialkylammonium alkyl group is an alkyl group which may have a substituent, in which at least one hydrogen atom is substituted with a trialkylammonium group, and preferably an alkyl group which may have a substituent, in which the hydrogen atom on the terminal carbon atom is substituted. The alkyl groups of the trialkylammonium groups may be the same or different.Examples of such groups include trimethylammonium methyl, trimethylammonium ethyl, triethylammonium methyl, triethylammonium ethyl, and tri-n-butylammonium methyl groups; carboxyalkyl groups (such as carboxymethyl, carboxyethyl, and carboxypropyl groups); hydroxyalkyl groups (such as hydroxymethyl, hydroxyethyl, and hydroxypropyl groups); alkoxyalkyl groups (such as methoxymethyl, ethoxymethyl, and 2-methoxypropan-2-yl groups); amidoalkyl groups (such as amidomethyl, amidoethyl, and dimethylamidomethyl groups); carboalkoxyalkyl groups (such as carbomethoxymethyl, carboethoxymethyl, carbomethoxyethyl, carboxyethoxyethyl, carboxymethoxypropyl, carboxymethoxyoctyl, carboxymethoxylauryl, and carboxymethoxy groups); Examples of the alkyl group include cystearyl group, carboxypropoxymethyl group, carboxypropoxyethyl group, carboxypropoxypropyl group, carboxyoctoxymethyl group, carboxylauroxymethyl group, carboxymyristoxymethyl group, carboxyoctoxyethyl group, carboxylauroxyethyl group, carboxystearoxyethyl group, etc.), aminoalkyl group (for example, aminomethyl group, aminoethyl group, dimethylaminomethyl group, etc.), alkylthioalkyl group (for example, methylthiomethyl group, ethylthiopropyl group, isopropylthioethyl group, etc.), alkoxycarbonylalkyl group (for example, methoxycarbonylmethyl group, ethoxycarbonylethyl group, methoxycarbonylethyl group, etc.), and sulfonatoalkyl group (for example, sulfonatomethyl group, 3-sulfonatopropyl group, 4-sulfonatobutyl group, 5-sulfonatopentyl group, 6-sulfonatohexyl group, etc.).

[0052] Unless otherwise specified in each description in this specification, the "aryl group" may have a substituent.

[0053] Examples of the aryl group which may have a substituent (preferably having 6 to 60 carbon atoms, more preferably having 6 to 30 carbon atoms, particularly preferably having 6 to 20 carbon atoms, and even more particularly preferably having 6 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a pentafluorophenyl group, a phenanthrenyl group, a pyrenyl group, a C1 to C6 12 Alkoxyphenyl group, C1-C 12 Alkylphenyl group, mono- or di-(C1-C 12 alkoxyphenyl)phenyl group, mono- or di-(C1-C 12 alkylphenyl)phenyl groups.

[0054] C1 to C 12 Alkoxy means that the alkoxy moiety has 1 to 12 carbon atoms (the same applies hereinafter).

[0055] C1 to C 12 Alkyl means that the alkyl moiety has 1 to 12 carbon atoms (the same applies hereinafter).

[0056] C1 to C 12 Examples of the alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a dimethoxyphenyl group, a propyloxyphenyl group, a 1,3,5-trimethoxyphenyl group, a methoxyethoxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group, a tert-butoxyphenyl group, a pentyloxyphenyl group, an isoamyloxyphenyl group, a hexyloxyphenyl group, a heptyloxyphenyl group, an octyloxyphenyl group, a nonyloxyphenyl group, a decyloxyphenyl group, and a dodecyloxyphenyl group.

[0057] C1 to C 12Examples of the alkylphenyl group include a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a mesityl group, a methylethylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a tert-butylphenyl group, a pentylphenyl group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, and a dodecylphenyl group.

[0058] Unless otherwise specified in each explanation in this specification, the "alkenyl group" may be straight-chain, branched or cyclic, and may have a substituent.

[0059] Examples of the alkenyl group which may have a substituent (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 15 carbon atoms, and even more particularly preferably having 2 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 1-cyclohexenyl group, a 1-norbornyl group, a 2-norbornyl group, and an arylalkenyl group. Examples of the arylalkenyl group include phenyl-C2-C 12 Alkenyl groups, C1-C 12 Alkoxyphenyl-C2-C 12 Alkenyl groups, C1-C 12 Alkylphenyl-C2-C 12 Alkenyl group, 1-naphthyl-C2-C 12 Alkenyl group, 2-naphthyl-C 12 Examples include alkenyl groups.

[0060] C2 to C 12 Alkenyl means that the alkenyl moiety has 2 to 12 carbon atoms (the same applies hereinafter).

[0061] Unless otherwise specified in each explanation in this specification, the "alkynyl group" may be straight-chain, branched or cyclic, and may have a substituent.

[0062] As the alkynyl group which may have a substituent (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent), for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butyn-1-yl group, a 3-butyn-1-yl group, or an arylalkynyl group is preferred. As the arylalkynyl group, for example, phenyl-C2-C 12 Alkynyl group, C1-C 12 Alkoxyphenyl-C2-C 12 Alkynyl group, C1-C 12 Alkylphenyl-C2-C 12 Alkynyl group, 1-naphthyl-C2-C 12 Alkynyl group, 2-naphthyl-C 12 Examples include alkynyl groups.

[0063] C2 to C 12 Alkynyl means that the alkynyl moiety has 2 to 12 carbon atoms (the same applies hereinafter).

[0064] Unless otherwise specified in each explanation in this specification, the "amino group" may be an unsubstituted amino group or an amino group substituted with one or two groups.

[0065] Examples of the optionally substituted amino group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 20 carbon atoms, and particularly preferably having 0 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituents) include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, an isopropylamino group, a diisopropylamino group, a butylamino group, an isobutylamino group, a tert-butylamino group, a pentylamino group, a hexylamino group, a cyclohexylamino group, a heptylamino group, an octylamino group, a 2-ethylhexylamino group, a nonylamino group, a decylamino group, a 3,7-dimethyloctylamino group, a laurylamino group, a cyclopentylamino group, a dicyclopentylamino group, a cyclohexylamino group, a dicyclohexylamino group, a pyrrolidyl group, a piperidyl group, a ditrifluoromethylamino group, a phenylamino group, a diphenylamino group, a C1-C 12 Alkoxyphenylamino group, di(C1-C 12 alkoxyphenyl)amino group, di(C1-C 12 alkylphenyl)amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C 12 Alkylamino group, C1-C 12 Alkoxyphenyl-C1-C 12 Alkylamino group, C1-C 12 Alkylphenyl-C1-C 12 alkylamino group, di(C1-C 12 Alkoxyphenyl-C1-C 12 alkyl)amino group, di(C1-C 12 Alkylphenyl-C1-C 12 alkyl)amino group, 1-naphthyl-C 12 Alkylamino group, 2-naphthyl-C1-C 12 Examples include alkylamino groups.

[0066] C1 to C 12Examples of the alkylamino group include a methylamino group, an ethylamino group, a dimethylamino group, a propylamino group, a 2,4,6-trimethylphenylthio group, a methylethylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a tert-butylamino group, a pentylamino group, an isoamylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, and a dodecylamino group.

[0067] The "heterocyclic group" used herein may have a substituent, unless otherwise specified in each description in this specification.

[0068] Examples of the optionally substituted heterocyclic group (preferably having 1 to 60 carbon atoms, more preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituents) include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group, a triazinyl group, and groups in which a hydrogen atom in these groups is replaced by an alkyl group (C1 to C 12 alkyl, etc.), alkoxy groups (C1-C 12 alkoxy groups, aryl groups, groups substituted with bromine atoms, etc.

[0069] Unless otherwise specified in each explanation in this specification, the "alkoxy group" may be straight-chain, branched or cyclic, and may have a substituent.

[0070] Examples of the alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) which may have a substituent include a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, a lauryloxy group, a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, a perfluorooctyl group, a methoxymethyloxy group, a 2-methoxyethyloxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0071] Unless otherwise specified in each explanation in this specification, the "alkylthio group" may be straight-chain, branched or cyclic, and may have a substituent.

[0072] Examples of the alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, an i-propylthio group, a butylthio group, an i-butylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group, a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group.

[0073] Unless otherwise specified in each description in this specification, the "aryloxy group" may have a substituent.

[0074] Examples of the optionally substituted aryloxy group (preferably having 6 to 60 carbon atoms, more preferably having 6 to 30 carbon atoms, particularly preferably having 6 to 20 carbon atoms, and even more particularly preferably having 6 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) include a phenoxy group, a C1-C 12 Alkoxyphenoxy group, C1-C 12 Examples thereof include an alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.

[0075] C1 to C 12 Examples of the alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a dimethoxyphenoxy group, a propyloxyphenoxy group, a 1,3,5-trimethoxyphenoxy group, a methoxyethoxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, a tert-butoxyphenoxy group, a pentyloxyphenoxy group, an isoamyloxyphenoxy group, a hexyloxyphenoxy group, a heptyloxyphenoxy group, an octyloxyphenoxy group, a nonyloxyphenoxy group, a decyloxyphenoxy group, and a dodecyloxyphenoxy group.

[0076] C1 to C 12 Examples of the alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, a butylphenoxy group, an isobutylphenoxy group, a tert-butylphenoxy group, a pentylphenoxy group, an isoamylphenoxy group, a hexylphenoxy group, a heptylphenoxy group, an octylphenoxy group, a nonylphenoxy group, a decylphenoxy group, and a dodecylphenoxy group.

[0077] Unless otherwise specified in the individual descriptions in this specification, the "arylthio group" may have a substituent.

[0078] The optionally substituted arylthio group (preferably having 6 to 60 carbon atoms, more preferably having 6 to 30 carbon atoms, particularly preferably having 6 to 20 carbon atoms, and even more particularly preferably having 6 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) includes a phenylthio group, a C1-C 12 Alkoxyphenylthio group, C1-C 12 Examples thereof include an alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0079] C1 to C 12 Examples of the alkoxyphenylthio group include a methoxyphenylthio group, an ethoxyphenylthio group, a dimethoxyphenylthio group, a propyloxyphenylthio group, a 1,3,5-trimethoxyphenylthio group, a methoxyethoxyphenylthio group, an isopropyloxyphenylthio group, a butoxyphenylthio group, an isobutoxyphenylthio group, a tert-butoxyphenylthio group, a pentyloxyphenylthio group, an isoamyloxyphenylthio group, a hexyloxyphenylthio group, a heptyloxyphenylthio group, an octyloxyphenylthio group, a nonyloxyphenylthio group, a decyloxyphenylthio group, and a dodecyloxyphenylthio group.

[0080] C1 to C 12 Examples of the alkylphenylthio group include a methylphenylthio group, an ethylphenylthio group, a dimethylphenylthio group, a propylphenylthio group, a mesitylthio group, a methylethylphenylthio group, an isopropylphenylthio group, a butylphenylthio group, an isobutylphenylthio group, a tert-butylphenylthio group, a pentylphenylthio group, an isoamylphenylthio group, a hexylphenylthio group, a heptylphenylthio group, an octylphenylthio group, a nonylphenylthio group, a decylphenylthio group, and a dodecylphenylthio group.

[0081] The "heterocyclic oxy group" used herein may have a substituent, unless otherwise specified in each description in this specification.

[0082] Examples of the optionally substituted heterocyclic oxy group (preferably having 1 to 60 carbon atoms, more preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms, and even more particularly preferably having 1 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) include a thienyloxy group, a C1-C 12 Alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C 12 Examples thereof include an alkylpyridyloxy group, an imidazolyloxy group, a pyrazolyloxy group, a triazolyloxy group, an oxazolyloxy group, a thiazoloxy group, and a thiadiazoleoxy group.

[0083] C1 to C 12 Examples of the alkylthienyloxy group include a methylthienyloxy group, an ethylthienyloxy group, a dimethylthienyloxy group, a propylthienyloxy group, a methylethylthienyloxy group, an isopropylthienyloxy group, a butylthienyloxy group, an isobutylthienyloxy group, a tert-butylthienyloxy group, a pentylthienyloxy group, an isoamylthienyloxy group, a hexylthienyloxy group, a heptylthienyloxy group, an octylthienyloxy group, a nonylthienyloxy group, a decylthienyloxy group, and a dodecylthienyloxy group.

[0084] C1 to C 12 Examples of the alkylpyridyloxy group include a methylpyridyloxy group, an ethylpyridyloxy group, a dimethylpyridyloxy group, a propylpyridyloxy group, a methylethylpyridyloxy group, an isopropylpyridyloxy group, a butylpyridyloxy group, an isobutylpyridyloxy group, a tert-butylpyridyloxy group, a pentylpyridyloxy group, an isoamylpyridyloxy group, a hexylpyridyloxy group, a heptylpyridyloxy group, an octylpyridyloxy group, a nonylpyridyloxy group, a decylpyridyloxy group, and a dodecylpyridyloxy group.

[0085] The "heterocyclic thio group" in this specification may have a substituent, unless otherwise specified in each description in this specification.

[0086] Examples of the heterocyclic thio group (preferably having 1 to 60 carbon atoms, more preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms, and even more particularly preferably having 1 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituents) include a thienylthio group, a C1-C 12 Alkylthienylthio group, pyrrolylthio group, furylthio group, pyridylmerthio group, C1-C 12 Examples thereof include an alkylpyridylthio group, a pyridazinylthio group, a pyrimidylthio group, an imidazolylthio group, a pyrazylthio group, a triazylthio group, an oxazolylthio group, a thiazolethio group, and a thiadiazolethio group.

[0087] C1 to C 12 Examples of the alkylthienylthio group include a methylthienylthio group, an ethylthienylthio group, a dimethylthienylthio group, a propylthienylthio group, a methylethylthienylthio group, an isopropylthienylthio group, a butylthienylthio group, an isobutylthienylthio group, a tert-butylthienylthio group, a pentylthienylthio group, an isoamylthienylthio group, a hexylthienylthio group, a heptylthienylthio group, an octylthienylthio group, a nonylthienylthio group, a decylthienylthio group, and a dodecylthienylthio group.

[0088] C1 to C 12 Examples of the alkylpyridylthio group include a methylpyridylthio group, an ethylpyridylthio group, a dimethylpyridylthio group, a propylpyridylthio group, a methylethylpyridylthio group, an isopropylpyridylthio group, a butylpyridylthio group, an isobutylpyridylthio group, a tert-butylpyridylthio group, a pentylpyridylthio group, an isoamylpyridylthio group, a hexylpyridylthio group, a heptylpyridylthio group, an octylpyridylthio group, a nonylpyridylthio group, a decylpyridylthio group, and a dodecylpyridylthio group.

[0089] The "carboxy group" in this specification may have a substituent, unless otherwise specified in each description in this specification.

[0090] Examples of the carboxy group which may have a substituent include an unsubstituted carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a heterocyclic oxycarbonyl group.

[0091] An alkoxycarbonyl group having 2 to 60 carbon atoms (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) which may have a substituent means a group in which an alkoxy group is bonded to a carbonyl group, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a neopentyloxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, and a dodecyloxycarbonyl group.

[0092] The aryloxycarbonyl group having 2 to 60 carbon atoms (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) which may have a substituent is a group composed of an aryloxy group which may have a substituent and a carbonyl group, and examples thereof include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a 2-methylphenoxycarbonyl group, a 4-chlorophenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, and a 3-phenoxyphenoxycarbonyl group.

[0093] The heterocyclic oxycarbonyl group having 2 to 60 carbon atoms (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms; these carbon numbers do not include the number of carbon atoms of the substituent) which may have a substituent is a group in which one hydrogen atom of a heterocyclic compound is substituted with an oxycarbonyl group, and examples thereof include a thienyloxycarbonyl group, a C1 to C 12 Alkylthienyloxycarbonyl group, pyrrolyloxycarbonyl group, furyloxycarbonyl group, pyridyloxycarbonyl group, C1-C 12Examples thereof include an alkylpyridyloxycarbonyl group, an imidazolyloxycarbonyl group, a pyrazolyloxycarbonyl group, a triazolyloxycarbonyl group, an oxazolyloxycarbonyl group, a thiazoleoxycarbonyl group, and a thiadiazoleoxycarbonyl group.

[0094] C1 to C 12 Examples of the alkylthienyloxycarbonyl group include a methylthienyloxycarbonyl group, an ethylthienyloxycarbonyl group, a dimethylthienyloxycarbonyl group, a propylthienyloxycarbonyl group, a methylethylthienyloxycarbonyl group, an isopropylthienyloxycarbonyl group, a butylthienyloxycarbonyl group, an isobutylthienyloxycarbonyl group, a tert-butylthienyloxycarbonyl group, a pentylthienyloxycarbonyl group, an isoamylthienyloxycarbonyl group, a hexylthienyloxycarbonyl group, a heptylthienyloxycarbonyl group, an octylthienyloxycarbonyl group, a nonylthienyloxycarbonyl group, a decylthienyloxycarbonyl group, and a dodecylthienyloxycarbonyl group.

[0095] C1 to C 12 Examples of the alkylpyridyloxycarbonyl group include a methylpyridyloxycarbonyl group, an ethylpyridyloxycarbonyl group, a dimethylpyridyloxycarbonyl group, a propylpyridyloxycarbonyl group, a methylethylpyridyloxycarbonyl group, an isopropylpyridyloxycarbonyl group, a butylpyridyloxycarbonyl group, an isobutylpyridyloxycarbonyl group, a tert-butylpyridyloxycarbonyl group, a pentylpyridyloxycarbonyl group, an isoamylpyridyloxycarbonyl group, a hexylpyridyloxycarbonyl group, a heptylpyridyloxycarbonyl group, an octylpyridyloxycarbonyl group, a nonylpyridyloxycarbonyl group, a decylpyridyloxycarbonyl group, and a dodecylpyridyloxycarbonyl group.

[0096] As used herein, examples of the "acyl group" include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

[0097] As used herein, examples of the "acyloxy group" include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

[0098] The term "amide group" as used herein also encompasses those having a substituent on the amide nitrogen atom (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, a fluorine atom, etc.).

[0099] Examples of the amide group which may have a substituent include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

[0100] As used herein, the term "acid imide group" refers to a monovalent residue obtained by removing one hydrogen atom bonded to the nitrogen atom from an acid imide. Examples of acid imide groups include groups represented by the following structural formula: In the structural formula, the line extending from the nitrogen atom represents a bond.

[0101] As used herein, the term "imine residue" refers to a monovalent residue obtained by removing one hydrogen atom from an imine compound (i.e., an organic compound having -N=C- in the molecule. Examples include aldimines, ketimines, and compounds in which the hydrogen atoms bonded to the nitrogen atoms in these molecules are substituted with alkyl groups or the like). Examples of imine residues include groups represented by the following structural formulas. The bond indicated by a wavy line in the structural formulas below means a "wedge-shaped bond" and / or a "dashed line bond." Here, a "wedge-shaped bond" means a bond extending outward from the plane of the paper, and a "dashed line bond" means a bond extending beyond the plane of the paper.

[0102] The "substituted silyl group" in this specification is preferably substituted with one or more of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group, and may be further substituted. Examples of the substituted silyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a tri-i-propylsilyl group, a t-butylsilyldimethylsilyl group, a triphenylsilyl group, a tri-p-xylylsilyl group, a tribenzylsilyl group, a diphenylmethylsilyl group, a t-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

[0103] The "substituted silyloxy group" in this specification is preferably substituted with one or more of an alkoxy group, an aryloxy group, an arylalkoxy group, and a monovalent heterocyclic oxy group, and may be further substituted. Examples of the substituted silyloxy group include a trimethylsilyloxy group, a triethylsilyloxy group, a tri-n-propylsilyloxy group, a tri-i-propylsilyloxy group, a t-butylsilyldimethylsilyloxy group, a triphenylsilyloxy group, a tri-p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a t-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

[0104] The "substituted silylthio group" in this specification is substituted with one or more of an alkylthio group, an arylthio group, an arylalkylthio group, and a monovalent heterocyclic thio group, and may be further substituted. Examples of the substituted silylthio group include a trimethylsilylthio group, a triethylsilylthio group, a tripropylsilylthio group, a tri-isopropylsilylthio group, a dimethyl-isopropylsilylthio group, a diethyl-isopropylsilylthio group, a tert-butylsilyldimethylsilylthio group, a pentyldimethylsilylthio group, a hexyldimethylsilylthio group, a heptyldimethylsilylthio group, an octyldimethylsilylthio group, a 2-ethylhexyldimethylsilylthio group, a nonyldimethylsilylthio group, a decyldimethylsilylthio group, a 3,7-dimethyloctyldimethylsilylthio group, a lauryldimethylsilylthio group, and a phenyl-C1-C 12 Alkylsilylthio group, C1-C 12 Alkoxyphenyl-C1-C 12 Alkylsilylthio group, C1-C 12 Alkylphenyl-C1-C 12 Alkylsilylthio group, 1-naphthyl-C1-C 12 Alkylsilylthio group, 2-naphthyl-C1-C 12 Alkylsilylthio group, phenyl-C1-C 12 Examples thereof include an alkyldimethylsilylthio group, a triphenylsilylthio group, a tri-p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

[0105] C1 to C 12 Examples of the alkylsilylthio group include a methylsilylthio group, an ethylsilylthio group, a dimethylsilylthio group, a propylsilylthio group, a methylethylsilylthio group, an isopropylsilylthio group, a butylsilylthio group, an isobutylsilylthio group, a tert-butylsilylthio group, a pentylsilylthio group, an isoamylsilylthio group, a hexylsilylthio group, a heptylsilylthio group, an octylsilylthio group, a nonylsilylthio group, a decylsilylthio group, and a dodecylsilylthio group.

[0106] C1 to C12 Examples of the alkyldimethylsilylthio group include a trimethylsilylthio group, an ethyldimethylsilylthio group, a propyldimethylsilylthio group, an isopropyldimethylsilylthio group, a butyldimethylsilylthio group, an isobutyldimethylsilylthio group, a tert-butyldimethylsilylthio group, a pentyldimethylsilylthio group, an isoamyldimethylsilylthio group, a hexyldimethylsilylthio group, a heptyldimethylsilylthio group, an octyldimethylsilylthio group, a nonyldimethylsilylthio group, a decyldimethylsilylthio group, and a dodecyldimethylsilylthio group.

[0107] The term "substituted silylamino group" as used herein refers to an amino group (-NH2) in which one or two hydrogen atoms have been substituted with a substituted silyl group. The substituted silylamino group may have a substituent other than a substituted silyl group in the amino group moiety, and examples of such a substituent include an alkyl group which may have a substituent and a monovalent heterocyclic group which may have a substituent.

[0108] Examples of the substituted silylamino group include a trimethylsilylamino group, a triethylsilylamino group, a tripropylsilylamino group, a triisopropylsilylamino group, a dimethylisopropylsilylamino group, a diethylisopropylsilylamino group, a tert-butylsilyldimethylsilylamino group, a pentyldimethylsilylamino group, a hexyldimethylsilylamino group, a heptyldimethylsilylamino group, an octyldimethylsilylamino group, a 2-ethylhexyldimethylsilylamino group, a nonyldimethylsilylamino group, a decyldimethylsilylamino group, a 3,7-dimethyloctyldimethylsilylamino group, a lauryldimethylsilylamino group, and phenyl-C1-C6 12 Alkylsilyloxy group, C1-C 12 Alkoxyphenyl-C1-C 12 Alkylsilylamino group, C1-C 12 Alkylphenyl-C1-C 12 Alkylsilylamino group, 1-naphthyl-C1-C 12 Alkylsilylamino group, 2-naphthyl-C1-C 12 Alkylsilylamino group, phenyl-C1-C12 Examples thereof include an alkyldimethylsilylamino group, a triphenylsilylamino group, a tri-p-xylylsilylamino group, a tribenzylsilylamino group, a diphenylmethylsilylamino group, a tert-butyldiphenylsilylamino group, and a dimethylphenylsilylamino group.

[0109] C1 to C 12 Examples of the alkylsilyloxy group include a methylsilyloxy group, an ethylsilyloxy group, a dimethylsilyloxy group, a propylsilyloxy group, a methylethylsilyloxy group, an isopropylsilyloxy group, a butylsilyloxy group, an isobutylsilyloxy group, a tert-butylsilyloxy group, a pentylsilyloxy group, an isoamylsilyloxy group, a hexylsilyloxy group, a heptylsilyloxy group, an octylsilyloxy group, a nonylsilyloxy group, a decylsilyloxy group, and a dodecylsilyloxy group.

[0110] C1 to C 12 Examples of the alkylsilylamino group include a methylsilylamino group, an ethylsilylamino group, a dimethylsilylamino group, a propylsilylamino group, a methylethylsilylamino group, an isopropylsilylamino group, a butylsilylamino group, an isobutylsilylamino group, a tert-butylsilylamino group, a pentylsilylamino group, an isoamylsilylamino group, a hexylsilylamino group, a heptylsilylamino group, an octylsilylamino group, a nonylsilylamino group, a decylsilylamino group, and a dodecylsilylamino group.

[0111] C1 to C 12 Examples of the alkyldimethylsilylamino group include a trimethylsilylamino group, an ethyldimethylsilylamino group, a propyldimethylsilylamino group, an isopropyldimethylsilylamino group, a butyldimethylsilylamino group, an isobutyldimethylsilylamino group, a tert-butyldimethylsilylamino group, a pentyldimethylsilylamino group, an isoamyldimethylsilylamino group, a hexyldimethylsilylamino group, a heptyldimethylsilylamino group, an octyldimethylsilylamino group, a nonyldimethylsilylamino group, a decyldimethylsilylamino group, and a dodecyldimethylsilylamino group.

[0112] In the present specification, the halogen atom is preferably a chlorine atom, a bromine atom, or a fluorine atom.

[0113] The present invention will be described in further detail below.

[0114] The present inventors have found that metal complexes represented by general formula (1) efficiently emit light in the visible light region (particularly the blue region). That is, when a 2,3'-bipyridine ligand having a specific structure forms a bond with M, the heavy atom effect promotes intersystem crossing from an excited singlet state to an excited triplet state, and as a result, the metal complexes of the present invention represented by general formula (1) efficiently emit phosphorescence in the visible light region. Furthermore, the present inventors have found that metal complexes represented by general formula (1) have very strong oxidizing power in the excited state and can be suitably used as photocatalysts.

[0115] The metal complex according to the present invention may contain geometric isomers.

[0116] The metal complex according to the present invention is a cationic metal complex and has a counter anion.

[0117] Among the metal complexes according to the present invention, those having a luminescence quantum yield in a room temperature solution (in air, an inert gas atmosphere or degassed conditions, preferably in an inert gas atmosphere or degassed conditions) of 0.01 or more are preferred, those having a luminescence quantum yield of 0.1 or more are more preferred, those having a luminescence quantum yield of 0.4 or more are particularly preferred, and those having a luminescence quantum yield of 0.5 or more are most preferred.

[0118] The measurement of the luminescence quantum yield in a room-temperature solution is preferably performed after bubbling an inert gas (argon gas, nitrogen gas) through the solution containing the dissolved metal complex to remove dissolved oxygen, or after freezing and degassing the solution containing the dissolved metal complex. The luminescence quantum yield can be measured using either the absolute method or the relative method. In the relative method, the luminescence quantum yield can be measured by comparing the luminescence spectrum with that of a standard substance (e.g., quinine sulfate). In the absolute method, measurement can be performed using a commercially available device (Hamamatsu Photonics Absolute PL Quantum Yield Measurement Device (C9920)). The luminescence quantum yield in a solution can be measured using various solvents, but the metal complex of the present invention may be measured in any solvent as long as the above-mentioned luminescence quantum yield is achieved.

[0119] Among the metal complexes of the present invention, those having an emission maximum wavelength (the peak wavelength on the shortest wavelength side) of an emission spectrum in a solution at room temperature are preferably in the range of 400 nm to 800 nm, more preferably in the range of 400 nm to 600 nm, particularly preferably in the range of 400 nm to 550 nm, and more particularly preferably in the range of 440 nm to 520 nm.

[0120] The redox potential of the compound of the present invention may be measured by a conventionally known method. For example, it can be measured by cyclic voltammetry (CV) with reference to the method described in "Electrochemical Measurement Methods (Vol. 1)" by Akira Fujishima, Masuo Aizawa, and Toru Inoue, published by Gihodo Publishing Co., Ltd. It is preferable to dissolve the compound of the present invention in an organic solvent containing a supporting electrolyte and measure it using a three-electrode system (working electrode, reference electrode, and counter electrode) under an inert gas atmosphere.

[0121] Examples of the organic solvent that can be used include acetonitrile, acetone, ethanol, ethylene glycol, ethylenediamine, dioxane, 1,2-dichloroethane, dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, sulfolane, propylene carbonate, tetrahydrofuran, 2,2,2-trifluoroethanol, toluene, pyridine, 1-propanol, 2-propanol, methanol, and N-methylacetamide. Among these, acetonitrile, N,N-dimethylformamide, dichloromethane, and tetrahydrofuran are preferred, and acetonitrile is more preferred.

[0122] Examples of the supporting electrolyte that can be used include tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetrahexylammonium perchlorate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetraethylammonium trifluoromethanesulfonate, and tetrabutylammonium trifluoromethanesulfonate. Among these, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, and tetrabutylammonium hexafluorophosphate are preferred, and tetrabutylammonium tetrafluoroborate is more preferred.

[0123] The working electrode may be a platinum electrode, a gold electrode, a carbon electrode, a mercury electrode, etc. Among these, a platinum electrode or a carbon electrode is preferred.

[0124] The reference electrode may be a silver-silver ion electrode, a silver-silver cryptate electrode, a silver-silver chloride electrode, or a Pt / I3 - , I - Electrodes, etc., are used. Among these, silver-silver ion electrodes are preferred. Examples of silver-silver ion electrodes include Ag / 0.01M AgNO3 + organic solvent (including a supporting electrolyte).

[0125] The counter electrode is made of platinum, carbon, etc. Among these, platinum is preferred.

[0126] It is also preferable to convert the oxidation-reduction potential obtained using a silver-silver ion electrode as a reference electrode to that of a saturated calomel electrode (SCE).

[0127] The reduction potential (E) in the ground state obtained by cyclic voltammetry (CV) red ) to the reduction potential (E red In addition, various methods are known for calculating the excitation energy (E'), and for example, it can be determined from the peak wavelength (the peak wavelength on the shortest wavelength side) of the emission spectrum at 77K.

[0128] The valence of the iridium atom is preferably trivalent.

[0129] The valence of the platinum atom is preferably divalent.

[0130] The metal complex according to the present invention is represented by general formula (1), and among these, metal complexes represented by general formulas (7) to (10) are preferred, metal complexes represented by general formula (7) or (8) are more preferred, and metal complexes represented by general formula (7) are particularly preferred.

[0131] General formula (7)

[0132] General formula (8)

[0133] General formula (9)

[0134] General formula (10)

[0135] The definitions of the symbols in the general formulae (7) to (10) are as described above, and the preferred ranges are also the same.

[0136] The compound of the present invention represented by the above general formula (1) can be produced, for example, as follows.

[0137] In the case where M = iridium, as shown in general formula (11), there is a method in which iridium chloride (III) is reacted with a 2,3'-bipyridine-based ligand to synthesize a chlorine-bridged iridium dimer as an intermediate, which is then reacted with silver trifluoromethanesulfonate and then reacted with L. Note that the counter anion is omitted here. Alternatively, the compound may be produced with reference to methods described in WO2002 / 015645, JP2017-226633, JP2015-189687, JP2021-113186, and the like.

[0138] General formula (11)

[0139] When M = platinum, as shown in general formula (12), there is a method in which platinum chloride (II) is reacted with a 2,3'-bipyridine-based ligand to synthesize an intermediate chlorine-bridged platinum dimer, which is then reacted with silver trifluoromethanesulfonate and then reacted with L. Note that the counter anion is omitted here. Alternatively, the compound may be produced with reference to the methods described in Dalton Transactions 2012, Vol. 41, p. 8077; Chemical Communications 2019, Vol. 55, p. 11191; Journal of Medicinal Chemistry 2023, Vol. 66, p. 13103, etc.

[0140] General formula (12)

[0141] The above reaction is preferably carried out under a nitrogen or argon atmosphere. The heating means is not particularly limited, but microwave irradiation is also preferred to facilitate the reaction. The microwave wavelength is not particularly limited, but is 2000 to 3000 MHz, preferably 2400 to 2500 MHz. Any commercially available organic synthesis reaction apparatus can be used as the microwave generator. An oil bath, mantle heater, or the like may also be used as the heating means. Examples of other reaction techniques include mechanochemical synthesis, which utilizes shaking, grinding, pressing, dispersion, kneading, and crushing using a shaker or ball mill, and electrolytic synthesis, which utilizes electrical current passing through electrodes.

[0142] In order to facilitate the reaction for synthesizing the metal complex according to the present invention, it is desirable to use a reaction solvent. Although there are no particular limitations on such a solvent, alcohol solvents, protic solvents, aprotic solvents, nitrile solvents, etc. are preferably used.

[0143] The metal complex according to the present invention can be subjected to post-treatment according to a conventional synthetic reaction, and then purified, if necessary, and used without purification. Examples of post-treatment methods include extraction, cooling, crystallization by adding water or an organic solvent, and distilling off the solvent from the reaction mixture, which can be used alone or in combination. Purification methods include recrystallization and column chromatography, which can be used alone or in combination.

[0144] Representative examples of the metal complexes represented by the general formula (1) according to the present invention are shown in Tables 1 and 2 below, but the present invention is not limited to these.

[0145] (Table 1)

[0146] (Table 2)

[0147] The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. Compounds appearing in the examples are shown in Tables 3 and 4.

[0148] (Table 3)

[0149] (Table 4)

[0150] Examples of synthesis of the compounds of the present invention are shown below.

[0151] Example 1-1 (Synthesis of Ligand 1) 2-Bromo-5-(trifluoromethyl)pyridine (3.40 g), 2,6-difluoropyridine-3-boronic acid (2.81 g), THF (75 mL), and a 2 M aqueous solution of potassium carbonate (30 mL) were placed in a three-neck flask. After argon gas was bubbled through the solution for 30 minutes, tetrakistriphenylphosphine(0)palladium (1.0 g) was added and the mixture was heated under reflux for 19 hours under an argon atmosphere. After cooling to room temperature, the organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: ethyl acetate:hexane=1:4 (v / v)), to obtain 4.1 g of Ligand 1. 1 The H-NMR data is shown below. 1 H-NMR (CDCl3): δ8.99 (s, 1H), 8.77 (q, 1H), 8.01-8.06 (m, 2H), 7.03 (dd, 1H).

[0152] Example 1-2 (Synthesis of Ligand 2) Methyl 2-chloro-5-(trifluoromethyl)pyridine-4-carboxylate (2.0 g), 2,6-difluoropyridine-3-boronic acid (1.46 g), THF (42 mL), and a 2 M aqueous solution of potassium carbonate (17 mL) were placed in a three-neck flask. After argon gas was bubbled through the solution for 30 minutes, tetrakistriphenylphosphine(0)palladium (0.556 g) was added and the mixture was heated under reflux for 72 hours under an argon atmosphere. After cooling to room temperature, the organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: ethyl acetate:hexane=1:4 (v / v)), to obtain Ligand 2. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d ６ ): δ9.20 (s, 1H), 8.84-8.91 (m, 1H), 8.22 (s, 1H), 7.30 (t, 1H), 3.99 (s, 3H).

[0153] Example 1-3 (Synthesis of Ligand 3) 2-Chloro-4,5-bis-(trifluoromethyl)pyridine (1.0 g), 2,6-difluoropyridine-3-boronic acid (0.7 g), THF (20 mL), and 2M aqueous potassium carbonate solution (8 mL) were placed in a three-neck flask. After argon gas was bubbled through this solution for 30 minutes, tetrakistriphenylphosphine(0)palladium (0.232 g) was added and the mixture was heated under reflux for 72 hours under an argon atmosphere. After cooling to room temperature, the organic layer was separated and collected, and separated and purified by silica gel chromatography (developing solvent: dichloromethane). Ligand 3 was obtained by further distillation under reduced pressure. 1 The H-NMR data is shown below. 1 H-NMR (CDCl ３ ): δ9.20 (s, 1H), 8.82 (q, 1H), 8.31 (s, 1H), 7.06 (dd, 1H).

[0154] Example 1-4 (Synthesis of Intermediate 1-1) Iridium chloride n-hydrate (442 mg), Ligand 1 (678 mg), 2-ethoxyethanol (48 mL), and water (17 mL) were placed in a three-neck flask and heated with stirring at 125°C for 41 hours under an argon atmosphere. After cooling to room temperature, the reaction solution was concentrated under reduced pressure, and water (30 mL) was added to the mixture. The resulting precipitate was collected by suction filtration and washed with water and methanol to obtain 0.70 g of Intermediate 1-1. The resulting solid was used in the next step without further purification.

[0155] Example 1-5 (Synthesis of Intermediate 2-1) Iridium chloride n-hydrate (963 mg), Ligand 2 (1.81 g), 2-ethoxyethanol (104 mL), and water (15 mL) were placed in a three-neck flask and heated with stirring at 125°C for 6 days under an argon atmosphere. After cooling to room temperature, the reaction solution was concentrated under reduced pressure, and water (30 mL) was added to the mixture. The resulting precipitate was collected by suction filtration and washed with water and methanol to obtain 2.35 g of Intermediate 2-1. The resulting solid was used in the next step without further purification.

[0156] Example 1-6 (Synthesis of Compound 1 of the Present Invention) A mixture of Intermediate 1-1 (394 mg), silver trifluoromethanesulfonate (145 mg), dichloromethane (35 mL), and methanol (10 mL) was heated and stirred at 45°C for 21 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain Intermediate 1-2. Subsequently, 4,4'-di-tert-butyl-2,2'-bipyridine (152 mg) and acetonitrile (16 mL) were added to Intermediate 1-2, and the mixture was heated and stirred at 90°C for 22 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and hexane to obtain 135 mg of Compound 1 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ8.96 (d, 2H), 8.64 (d, 2H), 8.51 (d, 2H), 8.31 (d, 2H), 7.88 (s, 2H), 7.80 (d, 2H), 6.14 (s, 2H), 1.43 (s, 18H).

[0157] Example 1-7 (Synthesis of Compound 2 of the Present Invention) A mixture of Intermediate 1-1 (197 mg), silver trifluoromethanesulfonate (72.5 mg), dichloromethane (18 mL), and methanol (5 mL) was heated and stirred at 45°C for 21 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain Intermediate 1-2. Subsequently, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (165 mg) and acetonitrile (16 mL) were added to Intermediate 1-2, and the mixture was heated and stirred at 90°C for 22 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 37 mg of Compound 2 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ9.51 (s, 2H), 8.79 (d, 2H), 8.64 (d, 2H), 8.51 (d, 2H), 8.22 (s, 2H), 8.12 (d, 2H), 6.12 (s, 2H).

[0158] Example 1-8 (Synthesis of Compound 3 of the Present Invention) A mixture of Intermediate 1-1 (197 mg), silver trifluoromethanesulfonate (72.5 mg), dichloromethane (18 mL), and methanol (5 mL) was heated and stirred at 45°C for 21 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain Intermediate 1-2. Subsequently, 5,5'-bis(trifluoromethyl)-2,2'-bipyridine (165 mg) and acetonitrile (16 mL) were added to Intermediate 1-2, and the mixture was heated and stirred at 90°C for 22 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 134 mg of Compound 3 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ9.37 (d, 2H), 8.87 (d, 2H), 8.67 (s, 2H), 8.62 (d, 2H), 8.50 (d, 2H), 8.24 (s, 2H), 6.10 (s, 2H).

[0159] Example 1-9 (Synthesis of Compound 4 of the Present Invention) A mixture of Intermediate 1-1 (197 mg), silver trifluoromethanesulfonate (72.5 mg), dichloromethane (18 mL), and methanol (5 mL) was heated and stirred at 45°C for 21 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain Intermediate 1-2. Subsequently, 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine (155 mg) and acetonitrile (12 mL) were added to Intermediate 1-2, and the mixture was heated and stirred at 90°C for 22 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 184 mg of Compound 4 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ9.42 (s, 2H), 8.65-8.62 (m, 4H), 8.51 (d, 2H), 8.16 (s, 2H), 8.14 (d, 2H), 6.12 (s, 2H), 4.01 (s, 6H).

[0160] Example 1-10 (Synthesis of Compound 5 of the Present Invention) A mixture of Intermediate 1-1 (197 mg), silver trifluoromethanesulfonate (72.5 mg), dichloromethane (18 mL), and methanol (5 mL) was heated and stirred at 45°C for 21 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain Intermediate 1-2. Subsequently, 4,4'-bis(hydroxymethyl)-2,2'-bipyridine (122 mg) and acetonitrile (12 mL) were added to Intermediate 1-2, and the mixture was heated and stirred at 90°C for 22 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 134 mg of Compound 5 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ8.85 (s, 2H), 8.63 (d, 2H), 8.49 (d, 2H), 8.29 (d, 2H), 8.08 (s, 2H), 7.72 (d, 2H), 6.11 (s, 2H), 5.03 (t, 2H), 4.95 (d, 4H).

[0161] Example 1-11 (Synthesis of Compound 6 of the Present Invention) A mixture of intermediate 1-1 (400 mg), silver trifluoromethanesulfonate (146.2 mg), dichloromethane (35 mL), and methanol (10 mL) was heated and stirred at 45°C for 18 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain intermediate 1-2. Subsequently, 4,4'-dimethoxy-2,2'-bipyridine (122 mg) and acetonitrile (15 mL) were added to intermediate 1-2, and the mixture was heated and stirred at 95°C for 67 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by silica gel chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 201 mg of the present compound 6. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ8.63 (d, 2H), 8.51 (d, 2H), 8.44 (d, 2H), 8.13 (d, 2H), 8.11 (s, 2H), 7.27 (dd, 2H), 6.10 (s, 2H), 4.11 (s, 6H).

[0162] Example 1-12 (Synthesis of Compound 7 of the Present Invention) A mixture of intermediate 1-1 (400 mg), silver trifluoromethanesulfonate (146.2 mg), dichloromethane (35 mL), and methanol (10 mL) was heated and stirred at 45°C for 18 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain intermediate 1-2. Subsequently, 4,4'-bis(N,N-dimethylamino)-2,2'-bipyridine (143.5 mg) and acetonitrile (15 mL) were added to intermediate 1-2, and the mixture was heated and stirred at 95°C for 19 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by alumina chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain 293 mg of the present compound 7. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ8.60 (d, 2H), 8.50 (d, 2H), 8.13 (s, 2H), 7.88 (d, 2H), 7.62 (d, 2H), 6.78 (d, 2H), 6.09 (s, 2H), 3.23 (s, 12H).

[0163] Example 1-13 (Synthesis of Compound 8 of the Present Invention) A mixture of intermediate 2-1 (400 mg), silver trifluoromethanesulfonate (133 mg), dichloromethane (35 mL), and methanol (10 mL) was heated and stirred at 45°C for 16 hours under an argon atmosphere. After cooling to room temperature, the mixture was filtered through a Celite pad, and the filtrate was concentrated under reduced pressure to obtain intermediate 2-2. Subsequently, 5,5'-bis(trifluoromethyl)-2,2'-bipyridine (150 mg) and acetonitrile (14 mL) were added to intermediate 2-2, and the mixture was heated and stirred at 95°C for 48 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration. A saturated aqueous solution of NH4PF6 was added to the filtrate, which was then concentrated under reduced pressure. Dichloromethane and water were then added for extraction. The organic layer was separated and collected, and purified by alumina chromatography (developing solvent: dichloromethane:acetone = 9:1 (v / v)). Further, reprecipitation was carried out using dichloromethane and diethyl ether to obtain Compound 8 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d ６ ): δ9.40 (d, 2H), 8.90 (d, 2H), 8.68 (s, 4H), 8.26 (s, 2H), 6.30 (s, 2H), 4.01 (s, 6H).

[0164] Example 1-14 (Synthesis of Compound 9 of the Present Invention) A mixture of intermediate 1-2 (115.0 mg), 2,2'-bipyridine-4,4'-dicarboxylic acid (31.9 mg), sodium acetate (41.7 mg), and methanol (15 mL) was heated and stirred at 75°C for 72 hours under an argon atmosphere. After cooling to room temperature, methanol was added and the solid obtained by filtration was washed with methanol. Compound 9 of the present invention was obtained by separation and purification using silica gel chromatography (developing solvent: dichloromethane containing 0.1% trifluoroacetic acid:methanol = 9:1 (v / v)). 1 The H-NMR data is shown below. 1 H-NMR (DMSO-d6): δ9.36 (s, 2H), 8.53 (d, 2H), 8.46 (d, 2H), 8.23 ​​(d, 2H), 8.02 (dd, 2H), 7.68 (s, 2H), 5.97 (s, 2H).

[0165] Example 1-15 (Synthesis of Compound 10 of the Present Invention) A mixture of intermediate 1-2 (72.8 mg), 4,4'-bis(trimethylaminomethyl)-2,2'-bipyridine dibromide (37.5 mg), and methanol (50 mL) was heated and stirred at 75°C for 72 hours under an argon atmosphere. After cooling to room temperature, the precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. The resulting solid was reprecipitated with methanol and diethyl ether, and then ethyl acetate and water were added for extraction. A saturated aqueous solution of NH4PF6 was added to the separated and recovered aqueous layer, and the resulting precipitate was washed with water and methanol to obtain Compound 10 of the present invention. 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ9.08 (s, 2H), 8.68 (d, 2H), 8.64 (d, 2H), 8.51 (d, 2H), 8.15 (d, 2H), 8.02 (s, 2H), 6.07 (s, 2H), 4.99 (m, 4H), 3.43 (s, 18H).

[0166] Example 1-16 (Synthesis of Compound 11 of the Present Invention) A mixture of intermediate 1-2 (114.9 mg), dipyridin-2-ylmethane (24.0 mg), and methanol (10 mL) was heated and stirred at 75°C for 72 hours under an argon atmosphere. After cooling to room temperature, saturated aqueous ammonium hexafluorophosphate solution was added and the mixture was filtered. The residue was washed with water and reprecipitated with acetone and diethyl ether. Compound 11 of the present invention was obtained by separation and purification using silica gel chromatography (dichloromethane:acetone = 9:1 (v / v)). 1 The H-NMR data is shown below. 1 H-NMR (acetone-d6): δ8.69 (d, 2H), 8.60 (d, 2H), 8.59 (s, 2H), 8.27 (d, 2H), 8.15 (t, 2H), 8.01 (d, 2H), 7.41 (t, 2H), 6.04 (s, 2H), 4.92 (s, 2H).

[0167] First, the emission spectrum of the compound of the present invention was measured at room temperature.

[0168] Example 2-1 (Emission of Compound 1 of the Present Invention at Room Temperature) Compound 1 of the present invention was dissolved in THF, and argon gas was bubbled through the solution. The emission spectrum was measured at room temperature using an absolute PL quantum yield measurement device (C9920, manufactured by Hamamatsu Photonics K.K.), and blue light was emitted (maximum emission wavelength λmax = 449 nm). The emission quantum yield was 0.77.

[0169] Comparative Example 2-1 (Emission of Comparative Compound 1 at Room Temperature) Comparative Compound 1 was dissolved in THF and argon gas was passed through the solution. The emission spectrum was measured at room temperature using an absolute PL quantum yield measurement device (C9920, manufactured by Hamamatsu Photonics K.K.), and light blue emission (maximum emission wavelength λmax=476 nm) was observed.

[0170] Comparative Example 2-2 (Emission of Comparative Compound 2 at Room Temperature) Comparative Compound 2 was dissolved in THF and argon gas was passed through the solution. The emission spectrum was measured at room temperature using an absolute PL quantum yield measurement device (C9920 manufactured by Hamamatsu Photonics K.K.), and blue-green emission (maximum emission wavelength λmax=480 nm) was observed.

[0171] From Example 2-1 and Comparative Example 2-1, it can be seen that the emission maximum wavelength of Compound 1 of the present invention is shifted 27 nm to a shorter wavelength than that of Comparative Compound 1, and Compound 1 of the present invention exhibits excellent performance as a blue light-emitting material. This is due to a remarkable electronic effect resulting from the replacement of the 2-phenylpyridine-based ligand of Comparative Compound 1 with a 2,3'-bipyridine-based ligand.

[0172] From Example 2-1 and Comparative Example 2-2, it can be seen that the emission maximum wavelength of Compound 1 of the present invention is shifted 31 nm shorter than that of Comparative Compound 2, and Compound 1 of the present invention exhibits excellent performance as a blue light-emitting material. This is due to a remarkable electronic effect resulting from the introduction of a trifluoromethyl group into a specific position (the 5-position of the pyridine ring forming the metal-nitrogen bond) of the 2,3'-bipyridine-based ligand of Comparative Compound 2.

[0173] Next, the emission spectrum of the compound of the present invention was measured at low temperature (77K).

[0174] Example 3-1 (Emission of Compound 1 of the Present Invention at 77 K) Compound 1 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). Intense blue emission was observed, with the shortest emission maximum wavelength λmax being 442 nm (equivalent to 2.81 eV in photon energy). The emission spectrum is shown in FIG.

[0175] Example 3-2 (Emission of Compound 2 of the Present Invention at 77 K) Compound 2 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 461 nm (equivalent to 2.69 eV in photon energy).

[0176] Example 3-3 (Emission of Compound 3 of the Present Invention at 77 K) Compound 3 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 456 nm (equivalent to 2.72 eV in photon energy).

[0177] Example 3-4 (Emission of Compound 4 of the Present Invention at 77 K) Compound 4 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 459 nm (equivalent to 2.70 eV in photon energy).

[0178] Example 3-5 (Emission of Compound 5 of the Present Invention at 77 K) Compound 5 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 442 nm (equivalent to 2.81 eV in photon energy).

[0179] Example 3-6 (Emission of Compound 6 of the Present Invention at 77 K) Compound 6 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 444 nm (equivalent to 2.80 eV in photon energy).

[0180] Example 3-7 (Emission of Compound 7 of the Present Invention at 77 K) Compound 7 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 453 nm (equivalent to 2.74 eV in photon energy).

[0181] Example 3-8 (Emission of Compound 8 of the Present Invention at 77 K) Compound 8 of the present invention was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, the compound exhibited strong blue emission, and the maximum emission wavelength λmax on the shortest wavelength side was 461 nm (equivalent to 2.69 eV in photon energy).

[0182] Comparative Example 3-1 (Emission of Comparative Compound 1 at 77 K) Comparative compound 1 was dissolved in 2-MeTHF and then cooled to 77 K using liquid nitrogen. The emission spectrum was measured using an absolute PL quantum yield measurement apparatus (C9920, manufactured by Hamamatsu Photonics K.K.). As a result, intense blue emission was observed, and the maximum emission wavelength λmax on the shortest wavelength side was 462 nm (equivalent to 2.68 eV in photon energy).

[0183] From Example 3-1 and Comparative Example 3-1, it was found that the maximum emission wavelength of Compound 1 of the present invention is 20 nm shorter than that of Comparative Compound 1, and therefore the energy level of the lowest excited triplet state (T1) of Compound 1 of the present invention is higher than that of Comparative Compound 1. In other words, this means that the excitation energy (E') of Compound 1 of the present invention is higher than that of Comparative Compound 1.

[0184] The electrochemical properties of the compound of the present invention were analyzed by cyclic voltammetry (CV). CV measurements were performed in acetonitrile using an electrochemical analyzer (manufactured by BAS Co., Ltd., model number: ALS Model 600C). In the measurements, the potential of the working electrode relative to the reference electrode (silver-silver ion electrode) was varied within an appropriate range to obtain the reduction potential (the potential required for one-electron reduction). Furthermore, the potential was converted using a saturated calomel electrode (SCE) as the reference.

[0185] The CV measurement conditions are as follows.

[0186] Solvent: acetonitrile, supporting electrolyte: tetrabutylammonium tetrafluoroborate 0.1 M), working electrode: platinum, reference electrode: Ag / AgNO3 (0.01 M), counter electrode: platinum, sweep rate: (0.2 V / sec), atmospheric gas: argon

[0187] Example 4-1 (CV Measurement of Compound 1 of the Present Invention) When the electrochemical properties of Compound 1 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-1.30 V vs. SCE.

[0188] Example 4-2 (CV Measurement of Compound 2 of the Present Invention) When the electrochemical properties of Compound 2 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-0.79 V vs. SCE.

[0189] Example 4-3 (CV Measurement of Compound 3 of the Present Invention) When the electrochemical properties of Compound 3 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-0.71 V vs. SCE.

[0190] Example 4-4 (CV Measurement of Compound 4 of the Present Invention) When the electrochemical properties of Compound 4 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-0.83 V vs. SCE.

[0191] Example 4-5 (CV Measurement of Compound 6 of the Present Invention) When the electrochemical properties of Compound 6 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-1.34V vs. SCE.

[0192] Example 4-6 (CV Measurement of Compound 7 of the Present Invention) When the electrochemical properties of Compound 7 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-1.43V vs. SCE.

[0193] Example 4-7 (CV Measurement of Compound 8 of the Present Invention) When the electrochemical properties of Compound 8 of the present invention were measured, it was found that the reduction potential in the ground state was E red =-0.70 V vs. SCE.

[0194] Comparative Example 4-1 (CV Measurement of Comparative Compound 1) When the electrochemical properties of Comparative Compound 1 were measured, the reduction potential in the ground state was found to be E red =-1.36V vs. SCE.

[0195] As described above, the reduction potential in the excited state (the potential required for one-electron reduction in the excited state) can be calculated by adding the excitation energy (E′) obtained from the emission spectrum at 77 K to the reduction potential in the ground state (the potential required for one-electron reduction in the ground state).

[0196] Example 5-1 (Reduction Potential of Compound 1 of the Present Invention in an Excited State) From the data of Examples 3-1 and 4-1, the reduction potential of Compound 1 of the present invention in an excited state was calculated as follows: E red * was calculated as +1.50 V vs. SCE.

[0197] Example 5-2 (Reduction Potential of Compound 2 of the Present Invention in an Excited State) From the data of Examples 3-2 and 4-2, the reduction potential of Compound 2 of the present invention in an excited state was calculated as follows: E red * was calculated as +1.90 V vs. SCE.

[0198] Example 5-3 (Reduction potential of compound 3 of the present invention in an excited state) From the data of Example 3-3 and Example 4-3, the reduction potential of compound 3 of the present invention in an excited state was red * was calculated as +2.01 V vs. SCE.

[0199] Example 5-4 (Reduction Potential of Compound 4 of the Present Invention in an Excited State) From the data of Examples 3-4 and 4-4, the reduction potential of Compound 4 of the present invention in an excited state was red * was calculated as +1.87 V vs. SCE.

[0200] Example 5-5 (Reduction Potential of Compound 6 of the Present Invention in an Excited State) From the data of Examples 3-6 and 4-5, the reduction potential of Compound 6 of the present invention in an excited state was calculated as follows: E red * was calculated to be +1.46 V vs. SCE.

[0201] <Examples 5-6 (Reduction Potential of Compound 7 of the Present Invention in an Excited State)> From the data of Examples 3-7 and 4-6, the reduction potential of Compound 7 of the present invention in an excited state was calculated as follows: E red * was calculated as +1.31 V vs. SCE.

[0202] <Examples 5-7 (Reduction Potential of Compound 8 of the Present Invention in an Excited State)> From the data of Examples 3-8 and 4-7, the reduction potential of Compound 8 of the present invention in an excited state was calculated as follows: E red * was calculated as +1.99 V vs. SCE.

[0203] Comparative Example 5-1 (Reduction Potential of Comparative Compound 1 in an Excited State) From the data of Comparative Examples 3-1 and 4-1, the reduction potential of Comparative Compound 1 in an excited state was red * was calculated as +1.32 V vs. SCE.

[0204] The results of Example 5-1 and Comparative Example 5-1 show that the reduction potential of Compound 1 in the excited state is about 0.18 V more positive than that of Comparative Compound 1, and that Compound 1 is more easily reduced in the excited state. This means that Compound 1 in the excited state has a stronger oxidizing power than Comparative Compound 1. It has been revealed that by substituting the phenylpyridine-based ligand of Comparative Compound 1, a known compound, with a 2,3'-bipyridine-based ligand, the oxidizing power in the excited state is dramatically strengthened.

[0205] Furthermore, from the results of Examples 5-1 to 5-7, when the compounds of the present invention are arranged in order of oxidizing power in the excited state, the order is Compound 3 of the present invention > Compound 8 of the present invention > Compound 2 of the present invention > Compound 4 of the present invention > Compound 1 of the present invention > Compound 6 of the present invention > Compound 7 of the present invention, which reveals that the introduction of an electron-withdrawing group into the 2,2'-bipyridine ligand dramatically strengthens the oxidizing power in the excited state.

[0206] Finally, in order to confirm whether the compound of the present invention functions as a photocatalyst, a photoreaction represented by the following formula (C) was carried out.

[0207] Example 6-1 (Photoreaction in nitrobenzene using compound 2 of the present invention) Formula (C) Three 20 mL vials containing transanethole (37 μL), styrene (290 μL), compound 2 of the present invention (2.8 mg), and nitromethane (4 mL) were prepared and stirred for 6 hours in a location exposed to sunlight. After the reaction was completed, the reaction solution was mixed. The reaction solution was evaporated under reduced pressure using an evaporator, and then separated and purified by silica gel chromatography (eluent: hexane / ethyl acetate = 10:1), obtaining product A with an isolation yield of 98.0%. 1 The H-NMR data is shown below. 1 H-NMR (CDCl3): δ7.28-7.23 (m, 2H), 7.20-7.13 (m, 5H), 6.84 (d, 2H), 3.79 (s, 3H), 3.39 (q, 1H), 2.94 (t, 1H), 2.52-2.48 (m, 1H), 2.37-2.28 (m, 1H), 1.70 (q, 1H), 1.18 (d, 3H).

[0208] Example 6-2 (Photoreaction in acetonitrile using Compound 2 of the Present Invention) A 20 mL vial containing trans-anethole (37 μL), styrene (290 μL), Compound 2 of the present invention (2.8 mg), and acetonitrile (4 mL) was stirred for 6 hours in a location exposed to sunlight. The reaction solution was evaporated under reduced pressure using an evaporator, and then separated and purified by silica gel chromatography (eluent: hexane / ethyl acetate=10:1), yielding Product A in an isolated yield of 99.9%.

[0209] Comparative Example 6-1 (Photoreaction in acetonitrile using comparative compound 1) A photoreaction was carried out in the same manner as in Example 6-2, except that comparative compound 1 was used instead of present invention compound 2, and product A was hardly obtained.

[0210] The results of Examples 6-1 and 6-2 revealed that Compound 2 of the present invention functions as a photocatalyst, and Product A is obtained almost quantitatively. On the other hand, in Comparative Example 6-1, Product A was hardly obtained. This is thought to be because the oxidizing power of Comparative Compound 1 used as a photocatalyst in the excited state is weaker than that of Compound 2 of the present invention, and therefore the reaction did not proceed.

[0211] From the above examples, it has been found that all of the metal complexes according to the present invention represented by general formula (1) exhibit strong luminescence in the visible light region (particularly the blue region) and have excellent properties such as strong oxidizing power in an excited state, and therefore can be suitably used as luminescent materials or photocatalysts for various applications.

Claims

1. A metal complex represented by the following general formula (1): (In general formula (1), M represents an iridium atom or a platinum atom, N represents a nitrogen atom, C represents a carbon atom, and F represents a fluorine atom. R a and R b each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. a and R b At least one of R is a halogen atom. 1 ~R 4 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. 2 and R 3 may be bonded to each other to form a ring structure. m represents 1 or 2. However, when M is an iridium atom, m is 2, and when M is a platinum atom, m is 1. X - represents a counter anion. L represents a neutral bidentate ligand that can form two M-nitrogen bonds.

2. R a and R b 2. The metal complex according to claim 1, wherein at least one of the following is a fluorine atom:

3. R a and R b The metal complex according to claim 2, wherein is a fluorine atom.

4. The metal complex according to claim 1, wherein L is 2,2'-bipyridine which may have a substituent.

5. The metal complex according to claim 4, wherein the 2,2'-bipyridine has one or more substituents selected from the group consisting of an alkyl group which may have a substituent, a carboxy group which may have a substituent, an amide group which may have a substituent, a halogen atom, or a trifluoromethyl group.

6. The metal complex according to claim 1, wherein M is an iridium atom.

7. A luminescent material comprising the metal complex according to any one of claims 1 to 6.

8. A photocatalyst comprising the metal complex according to any one of claims 1 to 6.

9. A metal complex represented by the following general formula (2): (In general formula (2), M represents an iridium atom or a platinum atom, N represents a nitrogen atom, C represents a carbon atom, and F represents a fluorine atom. Y represents a halogen atom. R a and R b each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. a and R b At least one of R is a halogen atom. 1 ~R 4 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, a carboxy group which may have a substituent, an acyl group, an acyloxy group, an amide group which may have a substituent, an acid imide group, an imine residue, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a halogen atom, a cyano group, a hydroxy group, or a trifluoromethyl group. 2 and R 3 may be bonded to each other to form a ring structure. m represents 1 or 2. However, when M is an iridium atom, m is 2, and when M is a platinum atom, m is 1.

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