Terbium complex and process for producing the same

Abstract

To provide at least one of a terbium complex which can be excited in a long wavelength region of ultraviolet light and has high luminous efficiency, an intermediate thereof and a method for producing the same.SOLUTION: The compound is represented by formula (1d). {wherein, HP is a hydroxypyranonato ligand represented by the formula (1hp). Wherein RA, RB, and RC each represent a specific substituent. )] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to terbium complexes and methods for making the same. [Background technology]

[0002] Optoelectronics, such as optical communications and displays, and the energy industry, including solar cells, are key technologies of the next generation. Various inorganic glass and ceramic materials, laser materials, organic small-molecule luminescent materials, and wavelength conversion materials have been developed for these applications. Wavelength conversion materials absorb light of a specific wavelength and emit light at another wavelength. They can be used as optical materials by adding them to resin materials. Terbium complexes with β-diketonato ligands have been reported as such wavelength conversion materials (e.g., Non-Patent Documents 1 and 2). These terbium complexes are capable of absorbing ultraviolet light and emitting green light, making them suitable for a variety of applications, including display phosphors, LED phosphors, solar cell films, and security inks. Maintaining high transparency after mixing wavelength conversion materials with resin materials is particularly essential for solar cell films and security inks. Therefore, terbium complexes, which have a larger Stokes shift than organic dyes, are suitable. Trivalent terbium complexes emit vivid green light through a luminescence mechanism in which the ligand absorbs light energy and transfers the energy to the terbium ion.

[0003] The terbium complexes described in Non-Patent Documents 1 and 2 are reported to exhibit high luminous efficiency in a solid state, an aqueous solution state, or at a low temperature of liquid nitrogen. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Coordination Chemistry Reviews, Vol. 293-294, p. 19 (2015) [Non-patent document 2] Communications Chemistry, Vol. 6, Article number 122 (2023) Summary of the Invention [Problem to be solved by the invention]

[0005] Under diluted conditions, such as in a solution or a resin film, most terbium complexes are generally excited by ultraviolet light of 350 nm or less, and it is difficult to maintain high luminescence efficiency in the long-wavelength region of ultraviolet light, with an excitation light source wavelength of more than 350 nm. Therefore, there has been a demand for terbium complexes under diluted conditions that can be excited by ultraviolet light of long wavelengths and have high luminescence efficiency.

[0006] An object of the present disclosure is to provide at least one of a terbium complex or an intermediate thereof that can be excited by ultraviolet light in the long wavelength region and has high luminescence efficiency, and a method for producing the same. [Means for solving the problem]

[0007] The present inventors have discovered that a terbium complex into which a specific ligand has been introduced exhibits strong luminescence, and have thus completed the present invention.

[0008] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows. [1] A terbium complex represented by the following formula (1d): [ka] {HP is a hydroxypyranonato ligand represented by formula (1hp). [ka] [In the formula, R Arepresents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluorocycloalkyl group having 3 to 8 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R B represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R C represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted, or a heteroaryl group having 3 to 9 carbon atoms which may be substituted. Also, R B and R C may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R A and R C cannot simultaneously be a methyl group.] n represents 1, 2, or 3. When n is 2 or 3, multiple HPs may be the same or different. m 1 represents 0, 1 or 2, m 2 represents 0, 1, 2 or 3, and 0≦m 1 +m 2 The relationship is ≦3. L 1 represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P=O groups. 1 When is 2, L 1 may be the same or different. L 2 represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m 2 When is 2 or 3, L 2 may be the same or different. X Lrepresents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms.}; [2]R B is a hydrogen atom, and R C is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a phenyl group which may be substituted with a halogen atom, or a pyridyl group which may be substituted with a halogen atom. [3] The terbium complex according to the above [1] or [2], wherein n is 3. [4]R A is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted with a substituent selected from substituent group T2A, or a heteroaryl group having 3 to 5 carbon atoms which may be substituted with a substituent selected from substituent group T2A, and substituent group T2A consists of an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a carbazol-9-yl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a cyano group, and a halogen atom. [5]m 1 The terbium complex according to any one of the above [1] to [4], wherein is 2. [6]L 1 is a phosphine oxide ligand represented by the following formula (3a): [ka] (In the formula, X A represents an alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, and may be the same or different. [7] An enol represented by the following formula (4d) and L 1phosphine oxides having one or two P=O groups represented by the formula (I) and (II); or nitrogen-containing compounds having two or more nitrogen atoms with unshared electron pairs and / or L 2 A method for producing a terbium complex (1d), comprising reacting a neutral compound represented by the formula (I) with a terbium compound. [ka] {HP is a hydroxypyranonato ligand represented by formula (1hp). [ka] [In the formula, R A represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluorocycloalkyl group having 3 to 8 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R B represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R C represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. Also, R B and R C may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R A and R C cannot simultaneously be a methyl group.] n represents 1, 2, or 3. When n is 2 or 3, multiple HPs may be the same or different. m 1 represents 0, 1 or 2, m 2 represents 0, 1, 2 or 3, and 0≦m 1 +m 2 The relationship is ≦3. L 1 represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P=O groups. 1 represents a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs or a phosphine oxide having one or two P=O groups. 1 When is 2, L 1 may be the same or different. L 2 represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. 2 ' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m 2 When is 2 or 3, L 2 may be the same or different. X L represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms.} [8] A diketonato complex represented by the following formula (1daq) and L 1 phosphine oxides having one or two P=O groups represented by the formula (I) or nitrogen-containing compounds having two or more nitrogen atoms with unshared electron pairs, or L 2 A method for producing a terbium complex (1d), comprising reacting a terbium complex (1d) with a neutral compound represented by the formula: [ka] {HP is a hydroxypyranonato ligand represented by formula (1hp). [ka] [In the formula, R Arepresents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R B represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R C represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted, or a heteroaryl group having 3 to 9 carbon atoms which may be substituted. Also, R B and R C may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R A and R C cannot simultaneously be a methyl group.] n represents 1, 2, or 3. When n is 2 or 3, multiple HPs may be the same or different. m 1 represents 0, 1 or 2, m 2 represents 0, 1, 2 or 3, and 0≦m 1 +m 2 The relationship is ≦3. L 1 represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P=O groups. 1 m' represents a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs or a phosphine oxide having one or two P=O groups. 1 When is 2, L 1 may be the same or different. L 2 represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. 2' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m 2 When is 2 or 3, L 2 may be the same or different. X L represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms. In the formula, Q 1 represents a neutral coordinate molecule, provided that m is not 0 and m 1 When is 0, Q 1 and L 2 are the same and m and m 2 are never the same. [9] An optical material comprising the terbium complex according to any one of [1] to [6] above.

[10] An optical material comprising the terbium complex according to any one of [1] to [6] above and one or more selected from a resin material, an inorganic glass, an organic low-molecular-weight material, and a solvent.

[11] The optical material according to the above

[10] , wherein the resin material is polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or a copolymer thereof; an epoxy resin; a polyimide resin; or a silicone resin.

[12] The optical material according to the above

[10] or

[11] , wherein the solvent is a halogenated hydrocarbon, an alcohol, an ester, a glycol ether, an ether, a ketone or a hydrocarbon.

[13] The optical material according to any one of [9] to

[12] above, which is a film for a solar cell, an agricultural film, an LED phosphor, a light-emitting material, a fluorescent material, or a wavelength conversion material. [Effects of the Invention]

[0009] The present disclosure can provide at least one of a terbium complex or an intermediate thereof that can be excited by ultraviolet light in the long wavelength region and has high luminescence efficiency, and a method for producing the same. [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows the emission spectrum of the terbium complex (1d-3) obtained in Example 1. [Figure 2] 1 shows the emission spectrum of the terbium complex (1d-8) obtained in Example 3. [Figure 3] 1 shows the emission spectrum of the terbium complex (1d-9) obtained in Example 4. [Figure 4] 1 shows the emission spectrum of the terbium complex (1d-10) obtained in Example 5. [Figure 5] 1 shows the emission spectrum of the terbium complex (1d-11) obtained in Example 6. [Figure 6] 1 shows the emission spectrum of the terbium complex (1d-12) obtained in Example 7. [Figure 7] 1 shows the emission spectrum of the terbium complex (1d-13) obtained in Example 9. [Figure 8] 1 shows the emission spectrum of the terbium complex obtained in Comparative Example 1. [Figure 9] 1 shows the emission spectrum of the terbium complex obtained in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure will be described in detail below. However, the embodiments described below are examples of the present disclosure, and the present disclosure is not limited to these contents. Furthermore, the configurations and parameters disclosed in this specification can be combined in any desired combination, and the upper and lower limits of the values ​​disclosed in this specification also include any combination in the present disclosure. Furthermore, in this specification, the term "optionally substituted" means that the compound may be substituted with one substituent, and that the compound may be substituted with two or more substituents. When the compound is substituted with two or more substituents, the compound may be substituted with one type of substituent or with multiple types of substituents. Furthermore, in this specification, the term "Tb 3+ " represents a trivalent terbium ion. In this specification, hydrogen atoms include deuterium atoms and tritium atoms.

[0012] The terbium complex according to this embodiment is represented by the following formula (1d). [ka]

[0013] HP and L in the terbium complex of this embodiment represented by formula (1d) (hereinafter also referred to as terbium complex (1d)) 1 , L 2 , m 1 , m 2 , n and X L The definitions of each will be explained below.

[0014] <HPについて> HP is a hydroxypyranonato ligand (hereinafter also referred to as hydroxypyranonato ligand (1hp)) represented by the formula (1hp). In the terbium complex (1d), the hydroxypyranonato ligand (1hp) is linked to Tb by one or two oxygen atoms. 3+Furthermore, depending on the structure of the tautomer of the hydroxypyranonato ligand (1hp), the following coordination structures of terbium complexes (1di) to (1dvi) exist. Although terbium complex (1d) encompasses all of terbium complexes (1di) to (1dvi), for convenience, these isomers are referred to as terbium complex (1d) in this specification.

[0015] As the coordination structure of the terbium complex (1d), the terbium complex (1di) or the terbium complex (1dii) is preferred in that it has optical properties suitable for use as an optically functional material. [ka] (In the formula, R A , R B , R C , L 1 , L 2 , m 1 , m 2 , n and X L is R in the above formula (1hp). A , R B , R C , L 1 , L 2 , m 1 , m 2 , n, and X L It has the same meaning as

[0016] Next, R in the hydroxypyranonato ligand (1hp) A , R B , and R C The definitions of each will be explained below.

[0017] (R A About R AThe alkyl group having 1 to 6 carbon atoms represented by the formula (I) may be either a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0018] R A Specific examples of the cycloalkyl group having 3 to 8 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0019] R AThe fluoroalkyl group having 1 to 6 carbon atoms and represented by the following formula is a group in which some or all of the hydrogen atoms in the alkyl group have been substituted with fluorine atoms. The fluoroalkyl group may be either a linear or branched fluoroalkyl group, and specific examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoropropan-2-yl group, a 2,2,2 -Trifluoro-1-(trifluoromethyl)ethyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,1,1,2,3,3,4,4,4-nonaorobutan-2-yl group, 1,1,1-trifluorobutan-2-yl group, 4,4,4-trifluorobutan-2-yl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5 ,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, perfluoropentan-2-yl group, 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentan-2-yl group, 1,1,2,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butyl group, 1,1,2,2,3,4,4,4-octafluoro-3-(trifluoromethyl)butyl group, 1,1,3,3,3-pentafluoro-2,2- Bis(trifluoromethyl)propyl group, 1,1,1,2,3,3,4,4,4-nonafluoro-1-(trifluoromethyl)butan-2-yl group, perfluorohexyl group, 1,1,1,2,3,3,4,4,5,5,6,6,6-decafluorohexan-2-yl group, 1,1,2,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentyl group, 1,1,2,2,3,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pentyl group, 1,1,2,2,3,3,4,5,5,Examples include a 5-decafluoro-4-(trifluoromethyl)pentyl group, a 1,1,1,2,2,3,3,4,4,5,5,5-dodecafluoro-1-(trifluoromethyl)pentan-2-yl group, a 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentan-2-yl group, a 1,1,1,2,2,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pentan-2-yl group, a 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl group, a 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, a 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group, and a perfluorocyclopentylmethyl group.

[0020] R A The fluorocycloalkyl group having 3 to 8 carbon atoms and represented by the following formula is a cycloalkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Specific examples of the fluorocycloalkyl group include a perfluorocyclopropyl group, a perfluorocyclobutyl group, a perfluorocyclopentyl group, and a perfluorocyclohexyl group.

[0021] R A Specific examples of the aryl group having 6 to 14 carbon atoms represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 9-anthryl group, a 2-phenanthrenyl group, a 3-phenanthrenyl group, and a 9-phenanthrenyl group.

[0022] R ASpecific examples of the heteroaryl group having 3 to 9 carbon atoms represented by the formula (I) include a triazinyl group, a furanyl group, a thienyl group, a pyrrolinyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a pyridyl group, a quinolinyl group, an isoquinolinyl group, a pyrazinyl group, a pyrimidyl group, a pyridazinyl group, a triazinyl group, a naphthyridinyl group, a cinnolinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, and a benzothiazolyl group.

[0023] R A The aryl group having 6 to 14 carbon atoms or the heteroaryl group having 3 to 9 carbon atoms represented by the following formula (I) may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a cycloalkyloxy group having 3 to 8 carbon atoms, an acyl group having 2 to 13 carbon atoms, a halogen atom, a cyano group, and an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms; an alkyloxy group having 1 to 6 carbon atoms; a cycloalkyloxy group having 3 to 8 carbon atoms; a fluoroalkyl group having 1 to 6 carbon atoms; a fluorocycloalkyl group having 3 to 8 carbon atoms; a fluoroalkyloxy group having 1 to 6 carbon atoms; Examples include one or more substituents selected from the group consisting of a fluorocycloalkyloxy group having 3 to 8 carbon atoms; an acyl group having 2 to 6 carbon atoms; and a diarylamino group having 12 to 24 carbon atoms which may be substituted with one or more halogen atoms or cyano groups (Group T21), and preferred are one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a carbazol-9-yl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a cyano group, and a halogen atom (Group T2A).

[0024] Examples of alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 3 to 8 carbon atoms in the T21 group include R A Examples of the substituents include those exemplified as the alkyl group having 1 to 6 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms in the above.

[0025] The alkyloxy group having 1 to 6 carbon atoms and belonging to Group T21 may be either a linear or branched alkyloxy group, and specific examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a 2-methylpropyloxy group, a 2,2-dimethylpropyloxy group, a 3-cyclopropylpropyloxy group, a 2-methylbutyloxy group, a 3-methylbutyloxy group, a tert-butyloxy group, a pentyloxy group, a 2-methylpentyloxy group, a 1-methylbutyloxy group, a 1,2-dimethylbutyloxy group, a 1-ethylpropyloxy group, and a hexyloxy group.

[0026] Specific examples of the cycloalkyloxy group having 3 to 8 carbon atoms belonging to Group T21 include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0027] The acyl group having 2 to 13 carbon atoms and belonging to Group T21 may be either an aliphatic acyl group or an aromatic acyl group. Specific examples include aliphatic acyl groups such as an acetyl group, an ethylcarbonyl group, a 1-propylcarbonyl group, an isopropylcarbonyl group, a 1-butylcarbonyl group, a 2-butylcarbonyl group, a tert-butylcarbonyl group, a 1-pentylcarbonyl group, a 2-pentylcarbonyl group, a 3-pentylcarbonyl group, and a 1-hexylcarbonyl group; and aromatic acyl groups such as a phenylcarbonyl group (benzoyl group), a 1-naphthylcarbonyl group, a 2-naphthylcarbonyl group, a (biphenyl-2-yl)carbonyl group, a (biphenyl-4-yl)carbonyl group, a (4-methylphenyl)carbonyl group, and a (2-methylphenyl)carbonyl group.

[0028] Examples of halogen atoms belonging to Group T21 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0029] Specific examples of diarylamino groups having 12 to 24 carbon atoms belonging to Group T21 include diphenylamino, N-(1-naphthyl)-N-phenylamino, and N-(2-naphthyl)-N-phenylamino. Two aryl groups may be linked together with the nitrogen atom to form a ring, and specific examples include carbazol-9-yl, iminostilbenyl, 9(10H)-acridonyl, 10,11-dihydro-5H-dibenzo[bf]azepinyl, and 10,11-dihydro-10-oxo-5H-dibenzo[bf]azepinyl.

[0030] The diarylamino group having 12 to 24 carbon atoms may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a cycloalkyloxy group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluorocycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyloxy group having 1 to 6 carbon atoms, a fluorocycloalkyloxy group having 3 to 8 carbon atoms, an acyl group having 2 to 6 carbon atoms, a halogen atom, and a cyano group.

[0031] The alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, the fluoroalkyl group having 1 to 6 carbon atoms, and the fluorocycloalkyl group having 3 to 8 carbon atoms include R A Examples of the substituents include those exemplified as the alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, the fluoroalkyl group having 1 to 6 carbon atoms, and the fluorocycloalkyl group having 3 to 8 carbon atoms in the above.

[0032] Examples of the alkyloxy group having 1 to 6 carbon atoms, the cycloalkyloxy group having 3 to 8 carbon atoms, and the halogen atom include the substituents exemplified as the alkyloxy group having 1 to 6 carbon atoms, the cycloalkyloxy group having 3 to 8 carbon atoms, and the halogen atom belonging to Group T21, respectively.

[0033] Specific examples of the acyl group having 2 to 6 carbon atoms include an acetyl group, an ethylcarbonyl group, a 1-propylcarbonyl group, an isopropylcarbonyl group, a 1-butylcarbonyl group, a 2-butylcarbonyl group, a tert-butylcarbonyl group, and a 1-pentylcarbonyl group.

[0034] The fluoroalkyloxy group having 1 to 6 carbon atoms may be either a linear or branched fluoroalkyloxy group. A Examples of the fluoroalkyl groups include those exemplified above, to which an oxygen atom is bonded.

[0035] Specific examples of the fluorocycloalkyloxy group having 3 to 8 carbon atoms include R A Examples of the fluorocycloalkyl groups include those exemplified above, to which an oxygen atom is bonded.

[0036] Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a butyl group, and a tert-butyl group.

[0037] Specific examples of the alkyloxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a 2-methylpropyloxy group, and a tert-butyloxy group.

[0038] R A is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted with a substituent selected from the above-mentioned substituent group T2A, or a heteroaryl group having 3 to 5 carbon atoms which may be substituted with a substituent selected from the above-mentioned substituent group T2A, in terms of optical properties suitable for an optical functional material; Ais more preferably a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a trifluoromethyl group, a difluoromethyl group, a perfluoropropyl group, a phenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group, a 4-bromophenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl group, a 4-(carbazol-9-yl)phenyl group, a 4-cyanophenyl group, a 2-furanyl group, or a 2-thienyl group, in terms of ease of synthesis.

[0039] (R B About R B Examples of the halogen atom represented by the formula: include the substituents exemplified as the halogen atoms belonging to group T21.

[0040] R B Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula: A Examples of the substituents include those exemplified as the alkyl group having 1 to 6 carbon atoms represented by the following formula:

[0041] R B Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R B Examples of the substituents include those exemplified as the cycloalkyl group having 3 to 8 carbon atoms represented by the following formula:

[0042] R B is preferably a hydrogen atom in terms of readily available raw materials.

[0043] (R C About R C As the alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, the aryl group having 6 to 14 carbon atoms, and the heteroaryl group having 3 to 9 carbon atoms, represented by the formula: AExamples of the substituent include the halogen atom represented by the following formula: an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 3 to 9 carbon atoms.

[0044] R C Examples of the halogen atom represented by the formula: include the substituents exemplified as the halogen atoms belonging to group T21.

[0045] R C The aryl group having 6 to 14 carbon atoms or the heteroaryl group having 3 to 9 carbon atoms represented by the following formula (I) may be substituted with a substituent. Examples of the substituent include one or more substituents selected from the above Group T21, and one or more substituents selected from the above Group T2A are preferred.

[0046] R C is preferably an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group which may be substituted with a halogen atom, or a pyridyl group which may be substituted with a halogen atom, in that it has optical properties suitable for an optical functional material, and is more preferably a methyl group in that the raw materials are easily available.

[0047] <nについて> n represents 1, 2, or 3. When n is 2 or 3, the multiple HPs may be the same or different. In terms of providing optical properties suitable for an optically functional material, n is preferably 3. In terms of ease of synthesis, when n is 2 or 3, it is preferable that the multiple HPs are the same.

[0048] <L 1 About > L 1 represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P=O groups.

[0049] In the terbium complex (1d) of the present invention, when a nitrogen-containing ligand having two or more nitrogen atoms with lone electron pairs is coordinated, the lone electron pairs of the nitrogen atoms in the nitrogen ligands are Tb3+Specific examples of the nitrogen-containing ligand include 1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,4,7,9-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline. 1,10-phenanthroline, 2-chloro-1,10-phenanthroline, 2,9-dichloro-1,10-phenanthroline, 4,7-dichloro-1,10-phenanthroline, 5-bromo-1,10-phenanthroline, 2-bromo-1,10-phenanthroline, 3-bromo-1,10-phenanthroline, 3,8-dibromo-1,10-phenanthroline, 4,7-dibromo-1,10-phenanthroline, 3,5,6,8-tetrabromo-1,10-phenanthroline, 5-hydroxy-1,10-phenanthroline, 4,7-dihydroxy-1,10- Phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 5-amino-1,10-phenanthroline, 5,6-diamino-1,10-phenanthroline, 5-nitro-1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, 2,2'-bipyridine, 2,2'-bipyridine-d8, 2,2'-bipyridine-6-carbonitrile, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'- Bipyridine, 4,4'-diamino-2,2'-bipyridine, 2,2'-bipyridyl-1,1'-dioxide, 2,2'-bipyridine-5,5'-diol, 6,6'-dicyano-2,2'-bipyridine, 4,4'-bis(dihydroxymethyl)-2,2'-bipyridine, 4,4'-dinonyl-2,2'-bipyridine, 4,4'-di(tert-butyl)-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 2,2':6'2''-terpyridine, 6-bromo-2,2'-bipyridine, 4-bromo-2,2'-bipyridine, 4,4'-Dibromo-2,2'-bipyridine, 5,5'-dibromo-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4',5,5'-tetramethyl-2,2'-bipyridine, 4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine, 4,4'-bis(dimethylamino)-2,2'-bipyridine, 4,4'-difluoro-2,2'-bipyridine, 5,5'-difluoro-2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine, 5,5'-bis(trifluoromethyl)-2 Examples of suitable amines include 2'-bipyridine, dimethyl-2,2'-bipyridine-4,4'-dicarboxylate, dimethyl-2,2'-bipyridine-5,5'-dicarboxylate, diethyl-2,2'-bipyridine-4,4'-dicarboxylate, diethyl-2,2'-bipyridine-5,5'-dicarboxylate, dipyrido[3,2-a:2',3'-c]phenazine, 2,2'-biquinoline, 4,5-diazafluoren-9-one, and N,N-diethyl-4-{[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazin-2-yl]}aniline.

[0050] In the terbium complex (1d) of this embodiment, L 1 is a phosphine oxide ligand having one or two P=O groups, the phosphine oxide ligand is represented by the following formula (3a) or formula (3b), and the lone electron pair of the oxygen atom bonded to the phosphorus atom is Tb 3+ It is coordinated to. [ka] [where, X A represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, and X may be the same or different. A may be an aryl group represented by the following formula (3c): [ka] (In the formula, X 1 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 3 to 9 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or a fluoroalkyloxy group having 1 to 6 carbon atoms, and the aryl group having 6 to 14 carbon atoms is optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkyloxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, and a nitro group (hereinafter sometimes referred to as "Group T23"). In formula (3b), X H represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, a cycloalkenylene group having 3 to 8 carbon atoms, an arylene group having 6 to 24 carbon atoms, or a heteroarylene group having 3 to 23 carbon atoms.]

[0051] (X A About X A The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be either a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 1-methylbutyl group, a 1,2-dimethylbutyl group, a 1-ethylpropyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decanyl group.

[0052] X ASpecific examples of the cycloalkyl group having 3 to 10 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, a bicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-2-yl group, an adamantan-1-yl group, an adamantan-2-yl group, and a bicyclo[2.2.1]heptan-2-yl group.

[0053] In terms of readily available raw materials, X in formula (3a) A is preferably an alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms.

[0054] X A is preferably a methyl group, an ethyl group, a butyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a tert-butyl group, or an adamantan-1-yl group in that the raw materials are readily available, and is more preferably a butyl group, an octyl group, or a cyclohexyl group in that the optical functional material has suitable optical properties.

[0055] (X 1 About X 1 Examples of the halogen atom represented by the formula: include the substituents exemplified as the halogen atoms belonging to group T21.

[0056] X 1 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula: A Examples of the substituent include those exemplified as the alkyl group having 1 to 6 carbon atoms represented by the following formula:

[0057] X 1Examples of the alkyloxy group having 1 to 6 carbon atoms represented by the following formula include the groups exemplified as the alkyloxy group having 1 to 6 carbon atoms belonging to Group T21.

[0058] X 1 The aryl group having 6 to 14 carbon atoms represented by R A Examples of the aryl group include the groups exemplified as the aryl group having 6 to 14 carbon atoms in the above.

[0059] X 1 As the heteroaryl group having 3 to 9 carbon atoms represented by the formula: A Examples of the heteroaryl group include those exemplified as heteroaryl groups having 3 to 9 carbon atoms represented by the following formula:

[0060] X 1 Specific examples of the aryloxy group having 6 to 14 carbon atoms represented by the formula: A Examples of the aryl groups include those exemplified above, to which an oxygen atom is bonded.

[0061] X 1 Examples of the fluoroalkyl group having 1 to 6 carbon atoms represented by the formula: A Examples include fluoroalkyl groups having 1 to 6 carbon atoms.

[0062] X 1 Examples of the fluoroalkyloxy group having 1 to 6 carbon atoms represented by the following formula include fluoroalkyloxy groups having 1 to 6 carbon atoms belonging to Group T21.

[0063] (X H About X H Specific examples of the alkylene group having 1 to 10 carbon atoms represented by the formula: A Examples of the alkyl groups include divalent groups obtained by removing one hydrogen atom from the alkyl groups exemplified above.

[0064] X H Specific examples of the cycloalkylene group having 3 to 8 carbon atoms represented by the formula: A Examples of the cycloalkyl groups include divalent groups obtained by removing one hydrogen atom from the cycloalkyl groups exemplified above.

[0065] X H The alkenylene group having 2 to 8 carbon atoms represented by the formula (I) may be either a linear or branched alkenylene group, and specific examples thereof include a vinylene group, a 1-methylvinylene group, a prop-1-ene-1,3-diyl group, a but-1-ene-1,4-diyl group, a butadiene-1,4-diyl group, a but-2-ene-1,4-diyl group, and a pent-1-ene-1,2-diyl group.

[0066] X in equation (3b) H Specific examples of the cycloalkenylene group having 3 to 8 carbon atoms represented by the formula (I) include a cyclopent-1-ene-1,2-diyl group, a cyclohex-1-ene-1,2-diyl group, and a cyclooct-1-ene-1,2-diyl group.

[0067] X H Specific examples of the arylene group having 6 to 24 carbon atoms represented by the formula (I) include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,8-diyl group, a phenanthrene-1,2-diyl group, a 9,10-phenanthrene-1,2-diyl group, a naphthacene-1,2-diyl group, a naphthacene-2,3-diyl group, a naphthacene-1,12-diyl group, a naphthacene-5,6-diyl group, a pyrene-1,6-diyl group, a pyrene-1,8-diyl group, a pyrene-2,7-diyl group, a biphenyl-2,2'-diyl group, a biphenyl-2,2'-diyl group, a ... Examples of suitable groups include chrysene-4,4'-diylurene group, biphenyl-2,3-diyl group, biphenyl-3,4-diyl group, p-terphenyl-4,4''-diyl group, m-terphenyl-4,4''-diyl group, p-terphenyl-3,3''-diyl group, o-terphenyl-4,4''-diyl group, o-terphenyl-3,3''-diyl group, chrysene-6,12-diyl group, coronene-1,8-diyltriphenylene-2,7-diyl group, binaphthyl-2,2'-diyl group, diphenylether-2,2'-diyl group, xanthene-4,5-diyl group, 9,9-dimethylxanthene-4,5-diyl group, and coronene-1,8-diyl group.

[0068] X H Specific examples of the heteroarylene group having 3 to 23 carbon atoms represented by the formula (I) include a furan-2,5-diyl group, a thiophene-2,5-diyl group, a benzo[b]thiophene-2,3-diyl group, a benzo[1,2-b:4,5-b]dithiophene-2,6-diyl group, a 9-phenylcarbazole-2,7-diyl group, a 9-phenylcarbazole-3,6-diyl group, a dibenzofuran-2,8-diyl group, a dibenzofuran-4,6-diyl group, a dibenzothiophene-2,8-diyl group, a dibenzothiophene-3,7-diyl group, a dibenzothiophene-4,6-diyl group, and a 1,10-phenanthroline-3,8-diyl group.

[0069] Therefore, L 1 More specifically, the phosphine oxide ligand having one or two P=O groups represented by the formula (I) includes triphenylphosphine oxide, cyclohexyldiphenylphosphine oxide, tri(p-tolyl)phosphine oxide, triphenylphosphine oxide-d 15, tributylphosphine oxide, tri(tert-butyl)phosphine oxide, trioctylphosphine oxide, tricyclohexylphosphine oxide, dicyclohexylphenylphosphine oxide, dicyclohexyl(o-tolyl)phosphine oxide, 2-biphenylyldicyclohexylphosphine oxide, tripentylphosphine oxide, 2-biphenylyldiphenylphosphine oxide, tri(o-tolyl)phosphine oxide, tris(2-methoxyphenyl)phosphine oxide, 1,2-bis(diphenylphosphinyl)ethane, 1,3-bis(diphenylphosphinyl)propane, 1,4-bis(diphenylphosphinyl)butane, 1,2-bis(dicyclohexyl) bis(diphenylphosphinyl)ethane, 1,2-bis(diphenylphosphinyl)benzene, 1,8-bis(diphenylphosphinyl)naphthalene, 6,6'-bis(diphenylphosphinyl)-2,2'-bipyridine, bis[2-[(oxo)diphenylphosphino]phenyl]ether, 1,1'-biphenyl-2,2'-diylbis(1,1-diphenylphosphine oxide), 2,2'-bis(diphenylphosphinyl)-1,1'-binaphthyl, 2,2'-bis(diphenylphosphinyl)-1,1'-binaphthyl, 4,5-bis(diphenylphosphinyl)-9,9-dimethylxanthene, and 4,5-bis[di(tert-butyl)phosphinyl]-9,9-dimethylxanthene.

[0070] L in formula (1d) 1 As the compound, a phosphine oxide ligand having one or two P=O groups (preferably, X Ais an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group represented by formula (3c); phenanthroline which may be substituted with one or more methyl groups or phenyl groups; bipyridine which may be substituted with one or more methyl groups or phenyl groups; or N,N-diethyl-4-{[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazin-2-yl]}aniline; dipyrido[3,2-a:2',3'-c]phenazine. In terms of ease of synthesis, X in formula (3a) and formula (3b) are preferred. A is an alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl group represented by formula (3c), and X H is more preferably an alkylene group having 1 to 4 carbon atoms; a diphenylether-2,2'-diyl group; a naphthalene-1,8-diyl group; a biphenyl-2,2'-diyl group; a binaphthyl-2,2'-diyl group; a bipyridine-2,2'-diyl group; or a xanthene-4,5-diyl group which may be substituted with one or more methyl groups. In terms of easy availability of raw materials, X in formula (3a) is A is particularly preferably an alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms.

[0071] Specific examples of the phenanthroline optionally substituted with one or more methyl groups or phenyl groups include 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, and 2,9-diphenyl-1,10-phenanthroline.

[0072] Specific examples of the bipyridine optionally substituted with one or more methyl groups or phenyl groups include 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, and 4,4',5,5'-tetramethyl-2,2'-bipyridine.

[0073] The alkyl group having 4 to 8 carbon atoms may be either a linear or branched alkyl group, and specific examples thereof include a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

[0074] Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a butane-1,2-diyl group, a butane-2,3-diyl group, and a 2-methylpropane-2,3-diyl group. In terms of easy availability of raw materials, the alkylene group having 1 to 4 carbon atoms is preferably a methylene group, an ethylene group, or a trimethylene group.

[0075] In addition, as the aryl group represented by formula (3c), in terms of the ease of availability of raw materials, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 2'-6'-dimethoxybiphenyl-2-yl group, a 2'-6'-diisopropoxy ... -yl group, 2'-4'-6'-tri(tert-butyl)biphenyl-2-yl group, 2-[3,5-diphenyl-1H-pyrazol-2-yl)]phenyl group, 3,5-bis(trifluoromethyl)phenyl group, 3,5-dimethylphenyl group, 4-chlorophenyl group, 2-bromophenyl group, 4-fluorophenyl group, perfluorophenyl group, 4-(trifluoromethyl)phenyl group, or 2'-methylbiphenyl-2-yl group is preferred.

[0076] <L 2 About > L 2 represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. In the terbium complex (1d) of this embodiment, when the neutral ligand is water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, ester compounds, carbonyl compounds, ether compounds, or alcohols, the lone electron pair on the oxygen atom in the neutral ligand is Tb 3+ When the neutral ligand is a nitrile compound, the unshared electron pair on the nitrogen atom of the cyano group is coordinated to the terbium ion.

[0077] L 2 When is a sulfoxide compound, specific examples of the sulfoxide compound include dimethyl sulfoxide and deuterated dimethyl sulfoxide.

[0078] L 2When is a sulfone compound, specific examples of the sulfone compound include dimethyl sulfone, diphenyl sulfone, and sulfolane.

[0079] L 2 When is an amide compound, specific examples of the amide compound include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

[0080] L 2 When is a nitrile compound, specific examples of the nitrile compound include acetonitrile, deuterated acetonitrile, propionitrile, and benzonitrile.

[0081] L 2 When is an ester compound, specific examples of the ester compound include ethyl acetate and ethyl benzoate.

[0082] L 2 When is a carbonyl compound, specific examples of the carbonyl compound include acetone, deuterated acetone, acetophenone, methyl ethyl ketone, benzaldehyde, acetaldehyde, and formaldehyde.

[0083] L 2 When is an ether compound, specific examples of the ether compound include diethyl ether, tetrahydrofuran, tetrahydrofuran-d8, and the like.

[0084] L 2 When is an alcohol, specific examples of the alcohol include methanol, deuterated methanol, ethanol, propanol, isopropyl alcohol, butanol, and tert-butyl alcohol.

[0085] L in formula (1d) 2As the solvent, acetone, deuterated acetone, acetonitrile, deuterated acetonitrile, methanol, deuterated methanol, ethanol, propanol, isopropyl alcohol, dimethyl sulfoxide, deuterated dimethyl sulfoxide, water, or heavy water is preferred in terms of easy availability of raw materials, and water is more preferred in terms of ease of synthesis.

[0086] <m 1 and m 2 About > m 1 represents 0, 1 or 2, m 2 represents 0, 1, 2 or 3, and 0≦m 1 +m 2 The relationship m is ≦3. 1 and m 2 As an optical functional material, m 1 is 1 or 2, and m 2 is preferably 0.

[0087] m 1 When is 2, L 1 may be the same or different. 1 are preferably the same.

[0088] <X L About > X L represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms.

[0089] X L Specific examples of the halide ion represented by the formula (I) include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

[0090] X LSpecific examples of the carboxylate ion represented by the formula (I) include saturated aliphatic carboxylate ions such as acetate ion, propionate ion, butyrate ion, isobutyrate ion, valerate ion, pivalate ion, and stearate ion; aromatic carboxylate ions such as benzoate ion and p-toluate ion; unsaturated aliphatic carboxylate ions such as acrylate ion and methacrylate ion; and heteroaromatic carboxylate ions such as nicotinate ion and isonicotinate ion.

[0091] X L Specific examples of the sulfonate ion represented by the formula (I) include organic sulfonate ions such as methanesulfonate ion, p-toluenesulfonate ion, benzenesulfonate ion, and trifluoromethanesulfonate ion; and inorganic sulfate ions such as hydrogen sulfate ion.

[0092] X L Specific examples of the β-diketonate ion having 5 to 12 carbon atoms represented by the formula (I) include an acetylacetonate ion, a hexafluoroacetylacetonate ion, a dibenzoylmethanate ion, a thenoyltrifluoroacetonate ion, and a 2-acetyl-5,5-dimethyl-1,3-cyclohexanedionate ion.

[0093] The terbium complex (1d) of this embodiment may contain a crystallization solvent used during purification by reprecipitation, recrystallization, or the like.

[0094] From the viewpoint of suitably realizing the luminescence phenomenon of the terbium complex of this embodiment, the energy level of the excited triplet level (T1) of the hydroxypyranonato ligand (1hp) of this embodiment is set to the lowest luminescence level of the terbium (III) ion. 5 It is preferable that it is higher than D4, specifically, it is preferable that it is 2.53 eV or more.

[0095] The T1 energy level of the hydroxypyranonato ligand (1hp) can be estimated using quantum chemical calculations. Specifically, it can be calculated by performing excited state calculations on the optimized structure using time-dependent density functional theory.

[0096] Specific examples of the terbium complex (1d) of this embodiment include terbium complexes represented by any of the following formulae (1d-1) to (1d-56) and (1daq-1) to (1daq-41). The T1 energy level of the hydroxypyranonato ligand (1hp) in each structure is also shown. In this specification, Me represents a methyl group, and Ph represents a phenyl group. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0097] Of the compounds represented by formulae (1d-1) to (1d-56) and (1daq-1) to (1daq-41), compounds represented by formulae (1d-1), (1d-3) to (1d-5), (1d-7) to (1d-22), (1daq-1), (1daq-3) to (1daq-5), or (1daq-7) to (1daq-9) are preferred in terms of easy availability of raw materials; compounds represented by formulae (1d-1), (1d-3), (1d-7) to (1d-16), (1daq-1), (1daq-3), (1daq-7), or (1daq-8) are more preferred in terms of ease of synthesis; and compounds represented by formulae (1d-3), (1d-8), (1d-11), or (1d-12) are even more preferred in terms of having optical properties suitable for use as optically functional materials.

[0098] <Method for producing terbium complex (1d)> Next, a method for producing the terbium complex (1d) will be described.

[0099] (Manufacturing method 1) The terbium complex (1d) can be produced by reacting an enol represented by the following formula (4d) (hereinafter also referred to as enol (4d)) with L 1 phosphine oxides having one or two P=O groups represented by the formula (I) and (II); or nitrogen-containing compounds having two or more nitrogen atoms with unshared electron pairs and / or L 2 One example of such a method is Production Method 1 (hereinafter also referred to as Method 1), which is characterized by reacting a neutral compound represented by the formula: [ka] (In the formula, R A , R B , R C , H.P., L. 1 , L 2 , X L , n, m 1 and m 2 is R in the formulas (1d) and (1hp). A , R B , R C , H.P., L. 1 , L 2 , XL , n, m 1 and m 2 It has the same meaning as L 1 L' represents a phosphine oxide having one or two P=O groups; or a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs. 2 ' represents a neutral compound.)

[0100] R in Method 1 A , R B , R C , H.P., L. 1 , L 2 , X L , n, m 1 and m 2 For definitions and specific examples, see R in the formulas (1d) and (1hp). A , R B , R C , H.P., L. 1 , L 2 , X L , n, m 1 and m 2 is the same as

[0101] L 1 Examples of the phosphine oxide having one or two P=O groups represented by formula (3a') include phosphine oxides represented by formula (3b') below (hereinafter referred to as phosphine oxide (3a') or phosphine oxide (3b')). [ka] (In the formula, X A represents X in the formulas (3a) and (3b). A In the formula, X H is X in the formula (3b) H It has the same meaning as

[0102] Phosphine oxide (3a') and phosphine oxide (3b') can be obtained by the method described in Chemical Reviews, Vol. 60, pp. 243-260, 1960. Alternatively, commercially available products may be used.

[0103] Specific examples of the phosphine oxide (3a') used in Method 1 include those represented by the following formulae (3a-1) to (3a-16). The present invention is not limited to these. Ph represents a phenyl group, Me represents a methyl group, and tBu represents a tert-butyl group. [ka]

[0104] Specific examples of the phosphine oxide (3b') used in Method 1 include one or more selected from the group consisting of the following formulae (3b-1) to (3b-13): [ka]

[0105] L in Method 1 2 ' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols.

[0106] L in Method 1 1 Specific examples of the nitrogen-containing compound having two or more nitrogen atoms with an unshared electron pair represented by ' include 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine-d8, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 5,5'-diphenyl-2,2'-bipyridine, and 4,4',5,5'-tetramethyl-2,2'-bipyridine. L in Method 1 2Specific examples of neutral compounds represented by ' include water, heavy water, acetone, deuterated acetone, methyl ethyl ketone, ethyl acetate, methanol, deuterated methanol, ethanol, propanol, isopropyl alcohol, acetonitrile, propionitrile, deuterated acetonitrile, diethyl ether, tetrahydrofuran, tetrahydrofuran-d8, 1,4-dioxane, dimethyl sulfoxide, deuterated dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, and sulfolane.

[0107] In Method 1, L 1 Nitrogen-containing compounds having two or more nitrogen atoms with unshared electron pairs represented by ' or L 2 As the neutral compound represented by formula (1), a commercially available product may be used.

[0108] The enol (4d) used in Method 1 can be obtained by a method described, for example, in The Journal of Organic Chemistry, Vol. 75, pp. 2741-2744, 2010; Journal of the American Chemical Society, Vol. 66, pp. 1220-1222, 1944; Tetrahedron, Vol. 74, pp. 2762-2768, 2018; The Journal of Organic Chemistry, Vol. 80, pp. 10643-10650, 2015. In Method 1, a commercially available product may be used as the enol (4d).

[0109] The enol (4d) used in Method 1 loses an active proton when treated with a base, and becomes an organic salt represented by the following formulas (4da) to (4dc). These organic salts (4da) to (4dc) may be used as the enol (4d). In this case, M', represented by the counter cation of the organic salts (4da) to (4dc), may be used. +Specific examples of the cation include alkali metal ions such as lithium ion, sodium ion, potassium ion, and cesium ion; tertiary ammonium ions such as triethylammonium, trimethylammonium, and diisopropylethylammonium; secondary ammonium ions such as diethylammonium and diisopropylammonium; pyridinium ions such as pyridinium and 2,6-dimethylpyridinium; imidazolium ions such as imidazolium and N-methylimidazolium; and ammonium ions. [ka] (In the formula, R A , R B and R C is R in equation (1hp) A , R B and R C It has the same meaning as M'. + represents a counter cation.)

[0110] Examples of the terbium compound used in Method 1 include halide salts such as terbium(III) fluoride, terbium(III) chloride, terbium(III) bromide, and terbium(III) iodide, or hydrates thereof; organic acid salts such as terbium(III) oxalate, terbium(III) acetate, terbium(III) trifluoroacetate, and terbium(III) trifluoromethanesulfonate, or hydrates thereof; metal alkoxides such as tris[N,N-bis(trimethylsilyl)amido]terbium(III), terbium(III) trimethoxide, terbium(III) triethoxide, and terbium(III) tri(isopropoxide); and inorganic acid salts such as terbium(III) phosphate, terbium(III) sulfate, and terbium(III) nitrate, or hydrates thereof. Among these, inorganic acid salts such as terbium(III) chloride and terbium(III) nitrate, or hydrates thereof; or organic acid salts such as terbium(III) oxalate, terbium(III) acetate, terbium(III) trifluoroacetate; and terbium(III) trifluoromethanesulfonate, or hydrates thereof; are preferred in terms of good reaction yield, and terbium(III) acetate; terbium(III) chloride; or terbium(III) nitrate, or hydrates thereof; are more preferred.

[0111] The terbium compound used in Method 1 can be a commercially available product.

[0112] In Method 1, L 1 ' and / or L 2' may be contained in the terbium compound used, and specific examples include inorganic salt hydrates such as terbium(III) acetate tetrahydrate, terbium(III) nitrate pentahydrate, and terbium(III) chloride hexahydrate, as well as complex compounds such as bis(triphenylphosphine oxide)terbium(III) chloride, bis(tricyclohexylphosphine oxide)terbium(III) chloride, bis[tri(o-tolyl)phosphine oxide]terbium(III) chloride, tris(triphenylphosphine oxide)terbium(III) chloride, bis(triphenylphosphine oxide)terbium(III) nitrate, bis(triphenylphosphine oxide)terbium(III) acetate, (phenanthroline)terbium(III) chloride, bis(phenanthroline)terbium(III) chloride, and (bipyridine)terbium(III) chloride. Among these, inorganic salt hydrates such as terbium(III) acetate tetrahydrate, terbium(III) nitrate hexahydrate, and terbium(III) chloride hexahydrate are preferred because the raw materials are readily available. The complex compounds can be obtained by methods such as those described in Journal of Rare Earths, Vol. 27, No. 3, p. 372 (2009) and Journal of Inorganic and General Chemistry, Vol. 619, No. 9, p. 1609 (1993). Commercially available products may also be used.

[0113] In Method 1, the reaction is preferably carried out in a solvent because it results in a good yield of the terbium complex (1d). There are no particular limitations on the type of solvent that can be used, as long as it does not inhibit the reaction. Examples of solvents that can be used include halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; esters such as methyl acetate, ethyl acetate, butyl acetate, and isoamyl acetate; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, tetrahydrofuran, and cyclopentyl methyl ether; ketones such as tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, and acetone; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, and xylene; and water. These solvents can be used alone or in combination in any ratio. The solvent is preferably dichloromethane, chloroform, methylcyclohexane, acetone, methanol, ethanol or water, as this provides a good reaction yield of the terbium complex (1d).

[0114] The molar ratio of the terbium compound and the enol (4d) in Method 1 will be described below. It is preferable to use 1.0 to 5.0 moles of the enol (4d), and more preferably 3.0 to 4.0 moles of the enol (4d), per mole of the terbium compound.

[0115] L in Method 1 1 When ' is phosphine oxide (3a'), the molar ratio of the terbium compound to the phosphine oxide (3a') will be explained below. It is preferable to use 0.5 to 5.0 moles of the phosphine oxide (3a'), and more preferably 1.0 to 3.0 moles of the phosphine oxide (3a'), per mole of the terbium compound.

[0116] L in Method 1 1 When terbium compound (3b') is phosphine oxide (3b'), the molar ratio of terbium compound to phosphine oxide (3b') is as follows: It is preferable to use 0.5 to 2.5 moles of phosphine oxide (3b'), more preferably 1.0 to 1.5 moles of phosphine oxide (3b'), per mole of terbium compound.

[0117] L in Method 1 1 When ' is a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs, the molar ratio between the terbium compound and the nitrogen-containing compound will be explained below. It is preferable to use 0.5 to 2.5 moles of the nitrogen-containing compound, and more preferably 1.0 to 1.5 moles of the nitrogen-containing compound, per mole of the terbium compound.

[0118] The molar ratio of the terbium compound and the neutral compound in Method 1 will be described below. It is preferable to use 0.5 to 10 moles of the neutral compound, and more preferably 1.0 to 8.0 moles of the neutral compound, per mole of the terbium compound.

[0119] m in Method 1 1 is 2, and two L 1 When the two L's are different, the terbium complex (1d) can be prepared. 1 They may be added simultaneously or separately.

[0120] In Method 1, a base may be added to promote the reaction. Examples of the base include organic amines such as trimethylamine, triethylamine, diethylamine, pyridine, and quinoline; or inorganic bases such as carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and ammonia. The equivalent amount of the base used is preferably 1.0 to 10 mol, more preferably 2.0 to 8.0 mol, and even more preferably 3.0 to 5.0 mol, per mol of the enol (4d).

[0121] In Method 1, the reaction temperature and reaction time are not particularly limited, and general conditions used by those skilled in the art when producing metal complexes can be used. As a specific example, terbium complex (1d) can be produced in good yield by appropriately selecting a reaction temperature of -80°C to 120°C and a reaction time of 1 minute to 120 hours.

[0122] The terbium complex (1d) produced by Method 1 can be purified by a purification method generally used by those skilled in the art for purifying metal complexes, appropriately selected and used. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, and column chromatography.

[0123] <Manufacturing method 2> The method for producing the terbium complex (1d) of this embodiment involves combining a diketonato complex represented by the following formula (1daq) with L 1 phosphine oxides having one or two P=O groups represented by the formula (I) or nitrogen-containing compounds having two or more nitrogen atoms with unshared electron pairs, or L 2 and a neutral compound represented by the formula (Id) above (hereinafter also referred to as Method 2). [ka] (In the formula, HP, L 1 , L 2 , X L , n, m 1 and m 2 are HP and L in Eq. (1d). 1 , L 2 , X L , n, m 1 and m 2 It has the same meaning as L 1 L' represents a phosphine oxide having one or two P=O groups; or a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs. 2 ' represents a neutral compound. Q 1 represents a neutral coordinate molecule, provided that m is not 0 and m 1 When is 0, Q 1 and L 2 are the same and m and m 2 are never identical.)

[0124] In Method 2, HP, L 1 , L 2 , X L , n, m 1 and m 2 The definitions and specific examples shown in the above formula (1d) are as follows: 1 , L 2 , X L , n, m 1 and m 2 is the same as

[0125] In Method 2, Q 1 Specific examples of the neutral coordinating molecule represented by the formula (I) include water, heavy water, pyridine, imidazole, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, propanol and isopropyl alcohol, nitriles such as acetonitrile and propionitrile, amines such as ammonia, diethylamine and triethylamine, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, and sulfur compounds such as dimethyl sulfoxide and dimethyl sulfone.

[0126] The diketonato complex (1daq) used in Method 2 can be obtained, for example, according to the method shown in Example 8.

[0127] Specific examples of the diketonato complex (1daq) used in Method 2 include structures represented by any of the above formulae (1daq-1) to (1daq-41).

[0128] L in Method 2 1 The phosphine oxide in which P=O is one or two groups can be represented by the phosphine oxides represented by the formula (3a') and formula (3b') (hereinafter referred to as phosphine oxide (3a') and phosphine oxide (3b')). In the case of phosphine oxide (3a') or phosphine oxide (3b'), the phosphine oxide (3a') or phosphine oxide (3b') to be used can be the same as those exemplified in the explanation of Method 1 above. Commercially available products can also be used.

[0129] L in Method 2 1 When ' is a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs, examples of the nitrogen-containing compound to be used include the same compounds as those exemplified in the explanation of Method 1 above.

[0130] L in Method 2 2 ' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols, and examples thereof include the same compounds as those exemplified in the description of Method 1 above.

[0131] In Method 2, carrying out the reaction in a solvent is preferred because it results in a good yield of terbium complex (1d). There are no particular limitations on the type of solvent that can be used, as long as it does not inhibit the reaction. Examples of solvents that can be used include halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; esters such as ethyl acetate, butyl acetate, and isoamyl acetate; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, and tetrahydrofuran; ketones such as tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, and acetone; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, and xylene; and water. These solvents can be used alone or in combination of two or more in any ratio. The solvent is preferably dichloromethane, chloroform, acetone, methylcyclohexane, methanol, ethanol or water, as this provides a good yield of the terbium complex (1d).

[0132] In Method 2, L 1 When ' is phosphine oxide (3a'), the molar ratio of the diketonato complex (1 daq) and the phosphine oxide (3a') will be described. It is preferable to use 0.5 to 5.0 moles of the phosphine oxide (3a'), and more preferably 1.0 to 3.0 moles of the phosphine oxide (3a'), per mole of the diketonato complex (1 daq).

[0133] In Method 2, L 1’When the diketonato complex (3b') is a phosphine oxide (3b'), the molar ratio of the diketonato complex (1 daq) to the phosphine oxide (3b') is as follows: It is preferable to use 0.5 to 2.5 moles of the phosphine oxide (3b'), and more preferably 1.0 to 1.5 moles of the phosphine oxide (3b'), per mole of the diketonato complex (3b').

[0134] In Method 2, L 1 When "'" is a nitrogen-containing compound having two or more nitrogen atoms with lone electron pairs, the molar ratio of the diketonato complex (1 daq) and the nitrogen-containing compound will be explained below. It is preferable to use 0.5 to 2.5 moles of the nitrogen-containing compound, and more preferably 1.0 to 1.5 moles of the nitrogen-containing compound, per mole of the diketonato complex (1 daq).

[0135] In Method 2, m 1 is 2, and two L 1 When the two L are different, the terbium complex (1d) can be prepared 1 may be added simultaneously or separately.

[0136] Diketonate complex (1 daq) and L in Method 2 1 The molar ratio of the neutral compound represented by ' will be explained below. It is preferable to use 0.5 to 10 moles of the neutral compound, and more preferably 1.0 to 8.0 moles of the neutral compound, per mole of the diketonato complex (1 daq).

[0137] In Method 2, the reaction temperature and reaction time are not particularly limited, and general conditions used by those skilled in the art when producing metal complexes can be used. As a specific example, terbium complex (1d) can be produced in a good reaction yield by selecting a reaction temperature of -80°C to 120°C and a reaction time of 1 minute to 120 hours.

[0138] The terbium complex (1d) produced by Method 2 can be purified by a purification method generally used by those skilled in the art for purifying metal complexes, such as filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, and column chromatography.

[0139] Enol (4d) can undergo isomerization to form enol (4di) or β-diketone (4dii). Although the present invention encompasses all of enol (4d), enol (4di), and β-diketone (4dii), for convenience, these isomers are referred to as enol (4d) in this specification. [ka] (In the formula, R A , R B and R C is R in the above formula (1hp) A , R B and R C It has the same meaning as

[0140] The diketonato complex (1daq) has the following coordination structures, diketonato complex (1daqi) to diketonato complex (1daqvi), depending on the structure of the tautomer of the hydroxypyronato ligand (1hp). Although the diketonato complex (1daq) encompasses all of the diketonato complexes (1daqi) to (1daqvi), for convenience, these isomers are referred to as the diketonato complex (1daq) in this specification. [ka] (In the formula, R A , R B , R C , X L , m, n and Q 1 is R in the above formulas (1daq) and (1hp). A , R B , R C , X L , m, n and Q1 It has the same meaning as

[0141] The terbium complex (1d) of this embodiment has high luminous efficiency and is therefore useful as an optical material containing the terbium complex (1d), and examples of such optical materials include luminescent materials, fluorescent materials, and wavelength conversion materials used therein, such as films for solar cells, agricultural films, LED phosphors, and security inks.

[0142] The terbium complex (1d) of this embodiment can be used as an optical material containing the terbium complex of this embodiment and one or more selected from a resin material, inorganic glass, an organic low-molecular-weight material, and a solvent. Because of its high dispersibility, it is particularly preferable to use it as an optical material containing a resin material. Examples of the resin material include polymethacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, fluorine-containing polymethyl methacrylate, fluorine-containing polyethyl methacrylate, fluorine-containing polypropyl methacrylate, fluorine-containing polyisopropyl methacrylate, fluorine-containing polybutyl methacrylate, fluorine-containing polysec-butyl methacrylate, fluorine-containing polyisobutyl methacrylate, and fluorine-containing polytert-butyl methacrylate; polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, and polyisobutyl acrylate. Examples of the polymerizable polymer include polyacrylates such as polytert-butyl acrylate, fluorine-containing polymethyl acrylate, fluorine-containing polyethyl acrylate, fluorine-containing polypropyl acrylate, fluorine-containing polyisopropyl acrylate, fluorine-containing polybutyl acrylate, fluorine-containing polysec-butyl acrylate, fluorine-containing polyisobutyl acrylate, and fluorine-containing polytert-butyl acrylate; polyolefins such as polystyrene, polyethylene, polypropylene, polybutene, fluorine-containing polyethylene, fluorine-containing polypropylene, and fluorine-containing polybutene; polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, and copolymers thereof; cellulose; polyacetal; polyester; polycarbonate; epoxy resin; polyamide resin; polyimide resin; polyurethane; Nafion; petroleum resin; rosin; and silicone resin.

[0143] Among these resin materials, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof; epoxy resins; polyimide resins; silicone resins, etc. are preferred. Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof; epoxy resins; polyimide resins; and silicone resins are particularly preferred. These may be used alone or in combination of two or more.

[0144] The content of the terbium complex (1d) in the optical material of this embodiment containing the terbium complex (1d) and a resin material is preferably 0.001 to 99% by weight, more preferably 0.01 to 50% by weight.

[0145] The inorganic glass may be any glass commonly used by those skilled in the art, such as soda glass, crystal glass, borosilicate glass, and the like.

[0146] The organic low molecular weight material may be any material commonly used by those skilled in the art, such as ionic liquids such as amyltriethylammonium bis(trifluoromethanesulfonyl)imide and tetraamylammonium chloride; or hydrocarbons such as pentadecane, hexadecane, octadecane, nonadecane, icosane, and paraffin.

[0147] Methods for obtaining an optical material containing the terbium complex (1d) of this embodiment include a method of using the terbium complex (1d) alone to produce an optical material; a method of incorporating the terbium complex (1d) into an optical material containing one or more selected from a resin material, an inorganic glass, and an organic low-molecular-weight material to produce an optical material; a method of mixing the terbium complex (1d) with a monomer corresponding to the resin material used in polymerizing the resin material and polymerizing the monomer to produce an optical material; and a method of dissolving and dispersing the terbium complex (1d) in a solvent to produce an optical material.

[0148] When the terbium complex (1d) of this embodiment is dissolved or dispersed in a solvent to form an optical material, examples of solvents that can be used include halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; esters such as ethyl acetate, butyl acetate, and isoamyl acetate; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, and tetrahydrofuran; ketones such as tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, and acetone; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, and xylene; and water. These solvents can be used alone or in combination of two or more in any ratio.

[0149] Among these solvents, halogenated hydrocarbons, alcohols, esters, glycol ethers, ethers, ketones, or hydrocarbons are preferred. [Example]

[0150] The present disclosure will be described below with reference to examples, but the present disclosure is not limited thereto.

[0151] The terbium complex (1d) was identified using the following analytical method. 1 H-NMR, 19 F-NMR and 31 P-NMR spectra were measured using ULTRASHIELD PLUS AVANCE III (400 MHz, 376 MHz, and 162 MHz) and ASCEND AVANCE III HD (400 MHz, 376 MHz, and 162 MHz) manufactured by BRUKER. 1 H-NMR was measured using deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6) as a measurement solvent and tetramethylsilane (TMS) as an internal standard. 19 F-NMR was measured using deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6) as the measurement solvent. 31 P-NMR was measured using deuterated chloroform (CDCl3) or deuterated acetone (Acetone-d6). Mass spectrometry was performed using a Waters Waters2695-micromass ZQ4000. Excitation and emission spectra were measured using a spectrophotometer (JASCO Corporation, FP-6500). UV-Vis spectra were measured using an ultraviolet-visible-near-infrared spectrophotometer (JASCO Corporation, V-670). Emission quantum yields were measured using an absolute PL quantum yield spectrometer (Hamamatsu Photonics, C11347-01). Commercially available reagents were used.

[0152] (Reference example 1) [ka] 4-Hydroxy-6-methyl-2-pyrone (2.52 g, 20.0 mmol) and benzoyl chloride (2.30 mL, 20.0 mmol) were dissolved in dichloromethane (64.0 mL) and cooled to -8 °C. N,N-Diisopropylethylamine (4.10 mL, 24.1 mmol) was added to this solution, and the mixture was stirred for 15.5 hours while slowly warming to room temperature. The reaction solution was diluted with chloroform (65.0 mL) and washed with 1 M hydrochloric acid (65.0 mL), saturated aqueous sodium bicarbonate solution (65.0 mL), and saturated brine (65.0 mL). The resulting organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a pale yellow solid. The resulting crude product was dissolved in acetonitrile (64.0 mL), and acetone cyanohydrin (2.00 mL, 21.9 mmol) and triethylamine (3.10 mL, 22.2 mmol) were added. The mixture was then stirred at 50 °C for 21 hours. 1 M hydrochloric acid (45.0 mL) and water (100 mL) were added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate (300 mL x 1, 100 mL x 1). The combined organic layers were washed with saturated brine (50.0 mL), dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was washed with methanol and dried under reduced pressure at 60 °C for 30 minutes to give 3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one as a pale yellow solid (yield 1.08 g, 24%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.95(brs,1H),7.64(brd,J=8.2Hz,2H),7.54(brd,J=7 .5Hz,1H),7.43(brdd,J=8.2,7.5Hz,2H),6.03(q,J=0.7Hz,1H),2.31(d,J=0.7Hz,3H).

[0153] (Reference example 2) [ka] Ethyl benzoylacetate (3.60 g, 18.7 mmol) and sodium hydroxide (1.55 g, 38.7 mmol) were dissolved in water (18.7 mL) and stirred at room temperature for 24 hours. The reaction mixture was washed three times with diethyl ether, and then 3 M hydrochloric acid was added under ice cooling until the pH reached approximately 1-2. The resulting white solid was collected by filtration, washed with water, and dried under reduced pressure to obtain a white solid of benzoylacetic acid. This crude product was used directly in the next reaction without further purification.

[0154] 1,1'-Carbonyldiimidazole (2.04 g, 12.6 mmol) and tetrahydrofuran (11.2 mL) were added to the resulting benzoylacetic acid and stirred at room temperature for 23 hours. 1 M hydrochloric acid was added to the reaction mixture until the pH reached approximately 1-2, and the mixture was extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine (20 mL), dried over sodium sulfate, and concentrated under reduced pressure to give 3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-one as a white solid (yield 1.46 g, 53%). 1 H-NMR (400MHz, CDCl3) δ (ppm): 15.94 (brs, 1H), 7.93-7.88 (m, 2H), 7.73-7.66 (m, 2H), 7.61-7.48 (m, 4H), 7.48-7.42 (m, 2H), 6.66 (s, 1H).

[0155] (Reference example 3) [ka] Terbium(III) acetate tetrahydrate (1.22 g, 3.00 mmol) and 2,2,6,6-tetramethyl-3,5-heptanedione (1.84 mL, 9.00 mmol) were dissolved in ethanol (22.4 mL) and water (7.50 mL). 1 M aqueous sodium hydroxide solution (9.00 mL, 9.00 mmol) was added and stirred at room temperature for 3 hours. Approximately half of the ethanol was removed by vacuum concentration. Water (50.0 mL) was added, and the precipitated solid was collected by suction filtration to give hexa[2,2,6,6-tetramethyl-3,5-heptanedionato]bisterbium(III) as a white solid (yield 2.17 g, 93%). ESIMS (m / z), MeOH: 1439.7 [M+Na] + ,525.4[M-2(2,2,6,6-tetramethyl-3,5-heptanedionato)] 2+ .

[0156] Example 1 [ka] Methanol (10.0 mL) was added to terbium acetate tetrahydrate (201 mg, 493 μmol) and triphenylphosphine oxide (275 mg, 988 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (340 mg, 1.48 mmol) obtained in Reference Example 1 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The insoluble solid was removed by filtration, the filtrate was added to water, and the precipitated solid was collected by suction filtration and washed with water to give a white solid, tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(triphenylphosphine oxide)terbium(III) (1d-3) (yield: 544 mg, 78%). ESIMS (m / z), MeOH: 1425.3 [M+Na] + ,1173.1[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0157] Example 2 [ka] Methanol (4.40 mL) was added to terbium acetate tetrahydrate (89.0 mg, 218 μmol) and triphenylphosphine oxide (121 mg, 436 μmol) and the mixture was stirred at room temperature for 1.5 hours. 3-Benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-one (193 mg, 660 μmol) obtained in Reference Example 2 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The precipitate in the reaction solution was collected by filtration, washed with methanol, and dried under reduced pressure to give bis(triphenylphosphine oxide)tris[3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-onato]terbium(III) (1d-7) as a white solid (yield: 161 mg, 46%). ESIMS (m / z), MeOH: 1611.3 [M+Na] + , 1333.2 [M-triphenylphosphine oxide + Na] + , 1297.2 [M—(3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-onato)] + .

[0158] Example 3 [ka] Methanol (5.00 mL) was added to terbium acetate tetrahydrate (102 mg, 251 μmol) and tricyclohexylphosphine oxide (149 mg, 501 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (172 mg, 748 μmol) obtained in Reference Example 1 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The insoluble solid was removed by filtration, the filtrate was added to water, and the precipitated solid was collected by suction filtration and washed with water to give tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(tricyclohexylphosphine oxide)terbium(III) (1d-8) as a white solid (yield: 250 mg, 69%). ESIMS (m / z), MeOH: 1460.9 [M+Na] + ,912.6[M-(tricyclohexylphosphine oxide)+Na] + .

[0159] Example 4 [ka] Methanol (5.00 mL) was added to terbium acetate tetrahydrate (103 mg, 253 μmol) and trioctylphosphine oxide (193 mg, 500 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (169 mg, 736 μmol) obtained in Reference Example 1 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The insoluble solid was removed by filtration, the filtrate was added to water, and the precipitated solid was collected by suction filtration and washed with water to give tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(trioctylphosphine oxide)terbium(III) (1d-9) as a white solid (yield: 388 mg, 95%). ESIMS (m / z), MeOH: 1614.1 [M+Na] + ,1254.5[M-(tricyclohexylphosphine oxide)+Na] + .

[0160] Example 5 [ka] Methanol (600 μL) was added to terbium acetate tetrahydrate (124 mg, 304 μmol) and tributylphosphine oxide (192 mg, 879 μmol) and stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 μmol) obtained in Reference Example 1 was added to the reaction mixture and stirred at room temperature for 3 hours. Water was added to the reaction solution, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give a white solid of tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(tributylphosphine oxide)terbium(III) (1d-10) (yield: 256 mg, 66%). ESIMS (m / z), MeOH: 1305.0 [M+Na] +,1053.5[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0161] Example 6 [ka] Methanol (600 μL) was added to terbium acetate tetrahydrate (123 mg, 300 μmol) and tri-o-tolylphosphine oxide (192 mg, 599 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 μmol) obtained in Reference Example 1 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give a white solid of tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(tri-o-tolylphosphine oxide)terbium(III) (1d-11) (yield: 406 mg, 91%). ESIMS (m / z), MeOH: 1510.5 [M+Na] + ,1257.4[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0162] Example 7 [ka] Methanol (600 μL) was added to terbium acetate tetrahydrate (123 mg, 300 μmol) and [1,1'-biphenyl]-2-yldiphenylphosphine oxide (96.0 mg, 271 μmol), and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 mmol) obtained in Reference Example 1 was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction solution, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis([1,1'-biphenyl]-2-yldiphenylphosphine oxide)terbium(III) (1d-12) as a white solid (yield: 457 mg, 98%). ESIMS (m / z), MeOH: 1578.6 [M+Na] + ,1325.5[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0163] Example 8 [ka] Terbium acetate tetrahydrate (124 mg, 304 μmol) and 3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 μmol) obtained in Reference Example 1 were dissolved in ethanol (3.00 mL) and water (1.00 mL) and stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure and washed with water to give diaquatris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]terbium(III) (1dq-3) as a white solid (yield 150 mg, 56%). ESIMS (m / z), MeOH: 869.1 [M-2H2O + Na] +Diaquatris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]terbium(III) and triphenylphosphine oxide (94.8 mg, 341 μmol) were added to ethanol (1.80 mL) and stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato]bis(triphenylphosphine oxide)terbium(III) (1d-3) as a white solid (yield 130 mg, 56%).

[0164] Example 9 [ka] Methanol (600 μL) was added to terbium acetate tetrahydrate (124 mg, 304 μmol) and 1,10-phenanthroline (54.1 mg, 300 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 mmol) obtained in Reference Example 1 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give a white solid of tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato](1,10-phenanthroline)terbium(III) (1d-13) (yield: 250 mg, 90%). ESIMS (m / z), MeOH: 1049.2 [M+Na] + ,797.2[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0165] Example 10 [ka] Methanol (600 μL) was added to terbium acetate tetrahydrate (123 mg, 300 μmol) and bis[2-[(oxo)diphenylphosphino]phenyl]ether (172 mg, 301 μmol), and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-methyl-2H-pyran-2-one (207 mg, 899 μmol) obtained in Reference Example 1 was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction solution, and the precipitated solid was collected by suction filtration and washed with 50% aqueous methanol to give tris[3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato](bis[2-[(oxo)diphenylphosphino]phenyl]ether)terbium(III) (1d-14) as a white solid (yield 374 mg, 88%). ESIMS (m / z), MeOH: 1440.3 [M+Na] + ,1187.3[M-(3-benzoyl-4-hydroxy-6-methyl-2H-pyran-2-onato)] + .

[0166] Example 11 [ka] Methanol (5.00 mL) was added to terbium acetate tetrahydrate (102 mg, 249 μmol) and 1,10-phenanthroline (44.3 mg, 246 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-one (215 mg, 736 μmol) obtained in Reference Example 2 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The insoluble solid was removed by filtration, the filtrate was added to water, and the precipitated solid was collected by suction filtration and washed with water to give a white solid, tris[3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-onato]1,10-phenanthroline terbium(III) (1d-15) (yield: 256 mg, 85%). ESIMS (m / z), MeOH: 1237.2 [M+Na] + ,1054.6[M-(1,10-phenanthroline)+Na] + .

[0167] Example 12 [ka] Methanol (5.00 mL) was added to terbium acetate tetrahydrate (102 mg, 251 μmol) and bis[2-(diphenylphosphino)phenyl]ether oxide (140 mg, 246 μmol) and the mixture was stirred at room temperature for 1 hour. 3-Benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-one (215 mg, 735 μmol) obtained in Reference Example 2 was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The insoluble solid was removed by filtration, the filtrate was added to water, and the precipitated solid was collected by suction filtration and washed with water to give tris[3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-onato]bis[2-(diphenylphosphino)phenyl]etheroxide terbium(III) (1d-16) as a white solid (yield: 305 mg, 76%). ESIMS (m / z), MeOH: 1624.5 [M+Na] + ,1311.1[M-(3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-onato)] + .

[0168] (Comparative Example 1) [ka] Methanol (5.00 mL) was added to terbium acetate tetrahydrate (408 mg, 1.01 mmol) and triphenylphosphine oxide (557 mg, 2.07 mol) and the mixture was stirred at room temperature for 1 hour. Hexafluoroacetylacetone (425 μL, 3.00 mmol) was added to the reaction mixture and the mixture was stirred at room temperature for 3 hours. The precipitated solid was collected by suction filtration and washed with a small amount of methanol to give a white solid of tris(hexafluoroacetylacetone)bis(triphenylphosphine oxide)terbium(III) (yield: 588 mg, 42%). 19 F-NMR(376MHz,CDCl3)δ(ppm):75.8(s,6F).ESIMS(m / z),MeOH:1359.1[M+Na] + .

[0169] (Comparative Example 2)

Chemical formula

[0170] <UV-Vis and Luminescence Spectrum Evaluation> Samples for measuring the UV-Vis spectrum and luminescence spectrum of the terbium complex obtained in the examples and the terbium complex obtained in the comparative examples were prepared by dissolving the terbium complexes obtained in Examples 1 to 12 and the terbium complexes obtained in Comparative Examples 1 and 2 in spectroscopic chloroform at a concentration of 0.01 mmol / L and filling them into a 1 cm spectroscopic quartz cell.

[0171] The measurement results of the UV-Vis spectrum and luminescence spectrum(excitation wavelength 350 nm) of the terbium complex obtained in the examples are shown in FIGS. 1 to 7. The measurement results of the UV-Vis spectrum and luminescence spectrum(excitation wavelength 300 nm) of the terbium complex obtained in the comparative examples are shown in FIGS. 8 and 9. The absorption edge on the long wavelength side in the UV-Vis spectrum is shown in Table 1.

[0172] <Luminescence Quantum Yield Evaluation> For the emission spectrum measurement and emission quantum yield evaluation samples of the terbium complexes obtained in the Examples and Comparative Examples, PMMA (polymethyl methacrylate) films containing 1.0 mass% of the terbium complexes obtained in the Examples and Comparative Examples were used. The PMMA film containing 1.0 mass% terbium complex was prepared by dissolving 4.5 mg of terbium complex and 445 mg of PMMA in 2 mL of chloroform, bar coating the obtained PMMA solution on a white glass plate, and air drying.

[0173] Table 1 shows the evaluation results of the luminescence quantum yields at an excitation wavelength of 350 nm (Ex350 nm) and 380 nm (Ex380 nm) of the terbium complexes obtained in the examples and comparative examples.

[0174] [Table 1]

[0175] As shown in Table 1, the terbium complex (1d) of this example can be excited by ultraviolet light in the long wavelength region and has high luminous efficiency. [Industrial Applicability]

[0176] The terbium complex (1d) of the present disclosure can be excited by long-wavelength ultraviolet light and has high luminescence efficiency, making it useful as a luminescent material, fluorescent material, or wavelength conversion material used in solar cell films, agricultural films, LED phosphors, security inks, and other applications.

Claims

1. A terbium complex represented by formula (1d): 【Chemistry 1】 {HP is a hydroxypyranonato ligand represented by formula (1hp)} 【Chemistry 2】 [In the formula, R Ａ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluorocycloalkyl group having 3 to 8 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R Ｂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R Ｃ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted, or a heteroaryl group having 3 to 9 carbon atoms which may be substituted. Also, R Ｂ and R Ｃ may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R Ａ and R Ｃ cannot simultaneously become a methyl group.] n represents 1, 2 or 3. When n is 2 or 3, the multiple HPs may be the same or different. m １ represents 0, 1 or 2, m ２ represents 0, 1, 2 or 3, and 0≦m １ +m ２ The relationship of ≦3 is satisfied. L １ represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P=O groups. １ When is 2, L １ may be the same or different. L ２ represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m ２ When is 2 or 3, L ２ may be the same or different. X Ｌ represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms.}

2. R Ｂ is a hydrogen atom, and R Ｃ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a phenyl group which may be substituted with a halogen atom, or a pyridyl group which may be substituted with a halogen atom.

3. 2. The terbium complex of claim 1, wherein n is 3.

4. R Ａ is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a substituent group T ２ an aryl group having 6 to 14 carbon atoms which may be substituted with a substituent selected from A, or a substituent group T ２ A is a heteroaryl group having 3 to 5 carbon atoms which may be substituted with a substituent selected from A, Said substituent group T ２ 2. The terbium complex according to claim 1, wherein A is an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a carbazol-9-yl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a cyano group, and a halogen atom.

5. m １ 2. The terbium complex according to claim 1, wherein R is 2.

6. L １ 2. The terbium complex according to claim 1, wherein is a phosphine oxide ligand represented by the following formula (3a): 【Transformation 3】 (In the formula, X Ａ represents an alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, and may be the same or different.

7. an enol represented by the following formula (4d) and L １ a phosphine oxide having one or two P=O groups represented by the formula (I)′; or a nitrogen-containing compound having two or more nitrogen atoms having an unshared electron pair and / or L ２ A method for producing a terbium complex (1d), comprising reacting a neutral compound represented by the formula (I) with a terbium compound. 【Chemistry 4】 {HP is a hydroxypyranonato ligand represented by formula (1hp)} 【Transformation 5】 [In the formula, R Ａ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluorocycloalkyl group having 3 to 8 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R Ｂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R Ｃ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted, or a heteroaryl group having 3 to 9 carbon atoms which may be substituted. Also, R Ｂ and R Ｃ may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R Ａ and R Ｃ cannot simultaneously become a methyl group.] n represents 1, 2 or 3. When n is 2 or 3, the multiple HPs may be the same or different. m １ represents 0, 1 or 2, m ２ represents 0, 1, 2 or 3, and 0≦m １ +m ２ The relationship of ≦3 is satisfied. L １ represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P═O groups. １ m' represents a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs or a phosphine oxide having one or two P=O groups. １ When is 2, L １ may be the same or different. L ２ represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. ２ ' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m ２ When is 2 or 3, L ２ may be the same or different. X Ｌ represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms.}

8. A diketonato complex represented by the following formula (1daq) and L １ a phosphine oxide having one or two P=O groups represented by the formula (I)′; or a nitrogen-containing compound having two or more nitrogen atoms having an unshared electron pair and / or L ２ ', and a neutral compound represented by the formula (1d). 【Transformation 6】 {HP is a hydroxypyranonato ligand represented by formula (1hp)} 【Transformation 7】 [In the formula, R Ａ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted heteroaryl group having 3 to 9 carbon atoms. R Ｂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. R Ｃ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted, or a heteroaryl group having 3 to 9 carbon atoms which may be substituted. Also, R Ｂ and R Ｃ may be taken together with the carbon atoms to which they are attached to form a 5-, 6-, or 7-membered ring. However, R Ａ and R Ｃ cannot simultaneously become a methyl group.] n represents 1, 2 or 3. When n is 2 or 3, the multiple HPs may be the same or different. m １ represents 0, 1 or 2, m ２ represents 0, 1, 2 or 3, and 0≦m １ +m ２ The relationship of ≦3 is satisfied. L １ represents a nitrogen-containing ligand having two or more nitrogen atoms with unshared electron pairs, or a phosphine oxide ligand having one or two P═O groups. １ m' represents a nitrogen-containing compound having two or more nitrogen atoms with unshared electron pairs or a phosphine oxide having one or two P=O groups. １ When is 2, L １ may be the same or different. L ２ represents a neutral ligand selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. ２ ' represents a neutral compound selected from the group consisting of water, heavy water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, ester compounds, carbonyl compounds, ether compounds, and alcohols. m ２ When is 2 or 3, L ２ may be the same or different. X Ｌ represents a halide ion, a nitrate ion, a carboxylate ion, a sulfonate ion, or a β-diketonate ion having 5 to 12 carbon atoms. In the formula, Q １ represents a neutral coordinate molecule, provided that m is not 0 and m １ When is 0, Q １ and L ２ are the same and m and m ２ are never the same.

9. An optical material comprising the terbium complex according to claim 1 .

10. An optical material comprising the terbium complex according to claim 1 and at least one selected from the group consisting of a resin material, an inorganic glass, an organic low-molecular-weight material, and a solvent.

11. 11. The optical material according to claim 10, wherein the resin material is polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or a copolymer thereof; an epoxy resin; a polyimide resin; or a silicone resin.

12. 11. The optical material according to claim 10, wherein the solvent is a halogenated hydrocarbon, an alcohol, an ester, a glycol ether, an ether, a ketone, or a hydrocarbon.

13. The optical material according to claim 10, which is a film for photovoltaic cells, an agricultural film, an LED phosphor, a light-emitting material, a fluorescent material, or a wavelength conversion material.

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