Rare earth complexes with an indanedione skeleton

Abstract

To provide a rare earth complex that is excitable by blue light and has high acid resistance, and a method for manufacturing the rare earth complex.SOLUTION: For example, there are provided rare earth complexes which respectively have specific structures represented by formulae (1a-1 to 1a-6).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a rare earth complex that can be excited by blue light and has excellent acid resistance. [Background technology]

[0002] Optoelectronics, such as optical communications and displays, and energy industries, such as solar cells, are key technologies of the next generation, and various inorganic glass materials, ceramic materials, laser materials, organic low-molecular-weight light-emitting materials, and wavelength conversion materials used in these industries are being created.

[0003] Wavelength conversion materials are materials that absorb light of a specific wavelength and emit light at a different wavelength, and can be used as optical materials by adding them to resin materials.

[0004] In recent years, rare earth complexes having β-diketonate ligands and phosphine oxide ligands (e.g., Patent Documents 1 and 2) and rare earth complexes having phenanthroline ligands (e.g., Non-Patent Document 1) have been reported as such wavelength conversion materials. These rare earth complexes can absorb short-wavelength light such as ultraviolet light and emit longer-wavelength visible light, so it is expected that by combining them with semiconductor light-emitting elements such as light-emitting diodes (LEDs), light-emitting devices with various emission colors can be realized (e.g., Patent Document 3).

[0005] Many of the rare-earth complexes mentioned above are excited and emit light by ultraviolet light (wavelengths of approximately 280 nm to 400 nm), but they are not excited and do not emit light by lower-energy blue light (approximately 450 nm to 495 nm). Therefore, they cannot be used as a light source with blue LEDs, which are normally used as excitation sources for LEDs. As a result, there is active research being done to develop rare-earth complexes that can be excited by blue light (for example, Non-Patent Documents 2 and 3).

[0006] On the other hand, in the application of rare earth complexes to industrial products, the stability of the rare earth complexes is often a challenge, as it is generally known that rare earth complexes decompose under acidic conditions. For example, epoxy resins, which are widely used as LED encapsulants, are obtained by mixing and heating epoxy resin as the main agent and acid anhydride as a curing agent, so the process involves acidic conditions (for example, Patent Document 4). In studies on using rare earth complexes in acidic resins, there have been reports of improving the acid resistance of rare earth complexes by adding surfactants, but the excitation wavelength of such rare earth complexes is limited to ultraviolet light, so their applications are limited (for example, Patent Document 5).

[0007] Furthermore, although the rare earth complexes disclosed in Non-Patent Documents 4, 5, and 6 are similar to the rare earth complexes described in this application, there is no description whatsoever regarding the acid resistance of these complexes. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] RUB1453860 [Patent Document 2] Japanese Patent Publication No. 2003-81986 [Patent Document 3] Japanese Patent Publication No. 2005-15564 [Patent Document 4] Japanese Patent Publication No. 2013-213220 [Patent Document 5] Japanese Patent Publication No. 2006-249231 [Non-patent literature]

[0009] [Non-Patent Document 1] CrystEngComm, No. 11, p. 1197 (2009) [Non-Patent Document 2] Coordination Chemistry Reviews, Vol. 293-294, p. 19 (2015) [Non-Patent Document 3] Angewandte Chemie International Edition, Vol. 43, p. 5010 (2004) [Non-Patent Document 4] Polyhedron, Volume 25, page 3488 (2008) [Non-Patent Document 5] Optical Materials, Vol. 32, p. 345 (2009) [Non-Patent Document 6] Dyes and Pigments, 2018, Vol. 159, p. 655 (2018) [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The object of this invention is to provide a rare earth metal complex that can be excited by blue light and has high acid resistance, as well as a method for producing the same. [Means for solving the problem]

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention discovered that rare-earth complexes into which specific ligands are introduced can be excited by blue light and have high acid resistance, thus completing the present invention.

[0012] In other words, the gist of the present invention is, [1] Rare earth complex represented by the following general formula (1a) (hereinafter also referred to as rare earth complex (1a)).

[0013] [ka]

[0014] {where, R Arepresents a C1-C6 haloalkyl group, naphthyl group, anthryl group, thienyl group, or furanyl group. Except for the haloalkyl groups, these groups may be substituted with one or more substituents selected from the group consisting of C1-C3 alkyl groups, C1-C3 fluoroalkyl groups, C1-C3 alkyloxy groups, C1-C3 fluoroalkyloxy groups, C5-C14 aryloxy groups, C1-C6 monoalkylamino groups, C5-C12 monoarylamino groups, C2-C12 dialkylamino groups, C10-C24 diarylamino groups, methylenedioxy groups, ethylenedioxy groups, halogen atoms, hydroxyl groups, nitro groups, and cyano groups (hereinafter sometimes referred to as the "T1 group"). Also, R A This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b).

[0015] [ka]

[0016] [In the formula, R 1 R represents a C1-C6 haloalkyl group, a C5-C4 aryl group, or a C4-C18 heteroaryl group, and these groups may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups (hereinafter sometimes referred to as the "T2 group"). 1 This represents an optionally substituted amino group shown by the following general formula (Z1).

[0017] [ka]

[0018] (In the formula, R Z1 and R Y1is, independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of 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, an alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group and a nitro group (hereinafter sometimes referred to as the "T3 group"). Further, R Z1 and R Y1 may form a ring together with the nitrogen atom to which they are attached.) Further, R 1 represents an optionally substituted oxy group represented by the following general formula (Y1).

[0019] [Chemical formula]

[0020] (In the formula, R X1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of 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, an alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group and a nitro group (hereinafter sometimes referred to as the "T4 group").)]

[0021] [Chemical formula]

[0022] [In the formula, R 2 represents a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an aryl group having a 5 to 14 carbon atoms, a heteroaryl group having 4 to 18 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, an alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group or a nitro group. Also, R 2 This represents an optional amino group shown by the general formula (Z2) below.

[0023] [ka]

[0024] (In the formula, R Z2 and R Y2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C4 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups (hereinafter sometimes referred to as the "T5 group"). Also, R Z2 and R Y2 (It may also form a ring with the bonded nitrogen atom.) Multiple R 2 These may be the same or different. Also, two adjacent Rs 2 It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R B R represents a hydrogen atom, deuterium atom, halogen atom, C1-C6 alkyl group, C1-C6 alkyloxy group, C2-C4 alkenyl group, C1-C6 haloalkyl group, C1-C6 monoalkylamino group, C5-C12 monoarylamino group, C2-C12 dialkylamino group, C10-C24 diarylamino group, cyano group, or nitro group. B They may be the same or different. Also, two adjacent Rs B It may also form a ring by being integrated with the bonded benzene ring. In the formula, m 1is an integer of 0, 1, or 2, and m 2 m is an integer, such that 0 ≤ m is 0, 1, 2, or 3. 1 +m 2 The relationship ≤ 3 is satisfied. In the formula, L 1 m represents a phosphine oxide ligand or nitrogen-containing ligand represented by the following general formula (3a) or general formula (3b). 1 When L is an integer of 2, multiple L 1 They may be the same or different.

[0025] [ka]

[0026] [ka]

[0027] [In the formula, X A X represents an alkyl group having 1 to 10 carbon atoms or an aryl group represented by the following general formula (3c). A They may be the same or different.

[0028] [ka]

[0029] (In the formula, X 1 X represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C5-C14 aryl group, a C4-C14 heteroaryl group, a C5-C14 aryloxy group, a C1-C6 haloalkyl group, or a C1-C6 haloalkyloxy group, and the C5-C14 aryl group may be substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkyloxy group, a hydroxyl group, a cyano group, and a nitro group (hereinafter sometimes referred to as the "T6 group"). 1(These may be the same or different.) In the formula, X H This represents an alkylidene group with 1 to 10 carbon atoms, an alkenylene group with 1 to 10 carbon atoms, an alkynylene group with 1 to 10 carbon atoms, an arylene group with 5 to 24 carbon atoms, or a heteroarylene group with 4 to 23 carbon atoms. In the formula, L 2 m represents a neutral ligand. 2 When is an integer of 2 or 3, multiple L 2 They may be the same or different. M represents rare earth ions. In the formula, X L This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents an integer of 0, 1, or 2. [2] The rare earth complex described in [1] above, n is 0. [3] The rare earth complex according to [1] or [2], wherein M is a europium ion, a terbium ion, or a gadolinium ion. [4]R B The rare earth complex described in any one of the above [1] to [3], wherein is a hydrogen atom, [5] R in the general formula (2a) 1 However, the rare earth complex according to any one of the above [1] to [4] is a C1-C4 alkyloxy group, a C2-C8 dialkylamino group, a phenothiazinyl group, a xanthenyl group, a phenoxazinyl group, a carbazoyl group, or a diphenylamino group (excluding the C1-C4 alkyloxy group and the C2-C8 dialkylamino group, these groups may be substituted with one or more substituents selected from the group consisting of a C1-C4 fluoroalkyl group, a C2-C5 alkylcarbonyl group, a C7-C13 arylcarbonyl group, a cyano group, and a nitro group). [6] E in the general formula (2b) is an oxygen atom, and R 2However, the rare earth complex described in any one of the above [1] to [5] is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a diphenylamino group, a phenoxy group, an alkylcarbonyl group having 2 to 5 carbon atoms, a cyano group, or a nitro group. [7] R of the general formula (2b) 2 However, the rare earth complex described in [6] above, which is a hydrogen atom, an alkyloxy group having 1 to 4 carbon atoms, or a nitro group, [8] The rare earth complex according to any one of the above [1] to [7], wherein the nitrogen-containing ligand is phenanthrene which may be substituted with a methyl group or a phenyl group, bipyridine which may be substituted with a methyl group or a phenyl group, or dipyrido[3,2-a:2',3'-c]phenazine which may be substituted with a methyl group or a phenyl group. [9] The rare earth complex according to any one of the above [1] to [8], wherein the neutral ligand is water.

[10] X in the above general formulas (3a) and (3b) A However, X is an alkyl group having 4 to 8 carbon atoms or an aryl group represented by the following general formula (3d), H The rare earth complex according to any one of the above [1] to [9], wherein is an alkylidene group having 1 to 4 carbon atoms; a diphenyl ether-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 xanthenediyl group which may be substituted with a methyl group.

[0030] [ka]

[0031] (In the formula, X 2 (This represents a hydrogen atom; a fluorine atom; a C1-C4 alkyl group; a C1-C4 alkyloxy group; a naphthyl group; a pyridyl group; a C1-C4 fluoroalkyl group; or a phenyl group which may be substituted with a fluorine atom, a C1-C4 alkyl group, a C1-C4 alkyloxy group, or a C1-C4 fluoroalkyl group.)

[11] X of the general formula (3d) 2The rare earth complex described in

[10] , wherein the hydrogen atom; a C1-C4 alkyl group; a C1-C4 alkyloxy group; or a phenyl group which may be substituted with a C1-C4 alkyl group or a C1-C4 alkyloxy group.

[12] m 1 is an integer of 1 or 2, and m 2 A rare earth complex according to any of the above [1] to [8],

[10] and

[11] , wherein is 0.

[13] Enols represented by the following general formula (4a) and L 1 Represented by; a phosphine oxide ligand represented by the following general formula (3a); a phosphine oxide ligand represented by the following general formula (3b); or a nitrogen-containing ligand or L 2 A method for producing a rare earth complex (1a), characterized by reacting a neutral ligand represented by with a rare earth compound,

[0032] [ka]

[0033] {where, R A R represents a C1-C6 haloalkyl group, naphthyl group, anthryl group, thienyl group, or furanyl group, and these groups, excluding the haloalkyl group, may be substituted with one or more substituents selected from the group consisting of C1-C3 alkyl groups, C1-C3 fluoroalkyl groups, C1-C3 alkyloxy groups, C1-C3 fluoroalkyloxy groups, C5-C14 aryloxy groups, C1-C6 monoalkylamino groups, C5-C12 monoarylamino groups, C2-C12 dialkylamino groups, C10-C24 diarylamino groups, methylenedioxy groups, ethylenedioxy groups, halogen atoms, hydroxyl groups, nitro groups, and cyano groups. A This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b).

[0034] [ka]

[0035] [In the formula, R 1 R represents a C1-C6 haloalkyl group, a C5-C4 aryl group, or a C4-C18 heteroaryl group, and these groups may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. 1 This represents an optionally substituted amino group shown by the following general formula (Z1).

[0036] [ka]

[0037] (In the formula, R Z1 and R Y1 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z1 and R Y1 It may form a ring together with the bonded nitrogen atom. ) Also, R 1 represents a substituted oxy group shown by the following general formula (Y1).

[0038] [ka]

[0039] (In the formula, R X1(These are a hydrogen atom, a C1-C6 alkyl group, or a C5-C4 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups.)

[0040] [ka]

[0041] [In the formula, R 2 This includes hydrogen atoms, deuterium atoms, halogen atoms, C1-C6 alkyl groups, C2-C4 alkenyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C5-C14 aryl groups, C4-C18 heteroaryl groups, and C5 This represents an aryloxy group with up to 14 carbon atoms, an alkylcarbonyl group with 2 to 7 carbon atoms, an arylcarbonyl group with 7 to 13 carbon atoms, a cyano group, or a nitro group. Also, R 2 This represents an optional amino group shown by the general formula (Z2) below.

[0042] [ka]

[0043] (In the formula, R Z2 and R Y2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z2 and R Y2 (It may also form a ring with the bonded nitrogen atom.) Multiple R 2 These may be the same or different. Also, two adjacent Rs 2 It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R B R represents a hydrogen atom, deuterium atom, halogen atom, C1-C6 alkyl group, C1-C6 alkyloxy group, C2-C4 alkenyl group, C1-C6 haloalkyl group, C1-C6 monoalkylamino group, C5-C12 monoarylamino group, C2-C12 dialkylamino group, C10-C24 diarylamino group, cyano group, or nitro group. B They may be the same or different. Also, two adjacent Rs B It may also form a ring by being integrated with the bonded benzene ring. In the formula, m 1 is an integer of 0, 1, or 2, and m 2 m is an integer, such that 0 ≤ m is 0, 1, 2, or 3. 1 +m 2 The relationship ≤ 3 is satisfied. In the formula, L 1 m represents a phosphine oxide ligand or nitrogen-containing ligand represented by the following general formula (3a) or general formula (3b). 1 When L is an integer of 2, multiple L 1 They may be the same or different.

[0044] [ka]

[0045] [ka]

[0046] [In the formula, X AX represents an alkyl group having 1 to 10 carbon atoms or an aryl group represented by the following general formula (3c). A They may be the same or different.

[0047] [ka]

[0048] (In the formula, X 1 X represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C1-C6 haloalkyl group, or a C1-C6 haloalkyloxy group, and the C5-C14 aryl group may be substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkyloxy group, a hydroxyl group, a cyano group, and a nitro group. 1 (These may be the same or different.) In the formula, X H This represents an alkylidene group with 1 to 10 carbon atoms, an alkenylene group with 1 to 10 carbon atoms, an alkynylene group with 1 to 10 carbon atoms, an arylene group with 5 to 24 carbon atoms, or a heteroarylene group with 4 to 23 carbon atoms. In the formula, L 2 m represents a neutral ligand. 2 When is an integer of 2 or 3, multiple L 2 They may be the same or different. In the formula, M represents a rare earth ion. In the formula, X L This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents an integer of 0, 1, or 2.

[14] A diketonate complex represented by the following general formula (1aq) and L 1represented by; a phosphine oxide ligand represented by the following general formula (3a); a phosphine oxide ligand represented by the following general formula (3b); or a nitrogen-containing ligand or L 2 A method for producing a rare earth complex (1a), characterized by reacting with a neutral ligand represented by

[0049] [Chemical formula]

[0050] {In the formula, R A represents a haloalkyl group having 1 to 6 carbon atoms, a naphthyl group, an anthryl group, a thienyl group, or a furanyl group, and these groups excluding the haloalkyl group may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a methylenedioxy group, an ethylenedioxy group, a halogen atom, a hydroxyl group, a nitro group, and a cyano group. Further, R A represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b).

[0051] [[ID=2']] [Chemical formula]

[0052] (In the formula, R 1 represents a haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a heteroaryl group having 4 to 18 carbon atoms, and these groups may be substituted with one or more substituents selected from the group consisting of 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, an alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Further, R 1represents an optionally substituted amino group represented by the following general formula (Z1).

[0053] [Chemical formula]

[0054] (In the formula, R Z1 and R Y1 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of 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, an alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group and a nitro group. Further, R<00000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​This represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C2-C4 alkenyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C2-C7 alkylcarbonyl group, a C7-C13 arylcarbonyl group, a cyano group, or a nitro group. Also, R 2 This represents an optional amino group shown by the general formula (Z2) below.

[0059] [ka]

[0060] (In the formula, R Z2 and R Y2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z2 and R Y2 (It may also form a ring with the bonded nitrogen atom.) Multiple R 2 These may be the same or different. Also, two adjacent Rs 2 It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R Brepresents a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a cyano group or a nitro group. A plurality of R B may be the same or different. Also, two adjacent R B may combine with the benzene ring to form a ring integrally. In the formula, m 1 is an integer of 0, 1 or 2, and m 2 is an integer of 0, 1, 2 or 3, and 0 ≦ m 1 + m 2 satisfies the relationship of ≦ 3. In the formula, L 1 represents a phosphine oxide ligand or a nitrogen-containing ligand represented by the following general formula (3a) or the following general formula (3b). When m 1 is an integer of 2, a plurality of L 1 may be the same or different.

[0061]

Chemical formula

[0062]

Chemical formula

[0063] [In the formula, X A represents an alkyl group having 1 to 10 carbon atoms or an aryl group represented by the following general formula (3c). A plurality of X A may be the same or different.

[0064]

Chemical formula

[0065] (In the formula, X 1X represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C1-C6 haloalkyl group, or a C1-C6 haloalkyloxy group, and the C5-C14 aryl group may be substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkyloxy group, a hydroxyl group, a cyano group, and a nitro group. 1 (These may be the same or different.) In the formula, X H This represents an alkylidene group with 1 to 10 carbon atoms, an alkenylene group with 1 to 10 carbon atoms, an alkynylene group with 1 to 10 carbon atoms, an arylene group with 5 to 24 carbon atoms, or a heteroarylene group with 4 to 23 carbon atoms. In the formula, L 2 m represents a neutral ligand. 2 When is an integer of 2 or 3, multiple L 2 They may be the same or different. In the formula, m represents an integer of 0, 1, 2, or 3. In the formula, Q 1 This represents a neutral molecule. However, m is not 0, but m 1 When Q is 0, 1 and L 2 They are identical and m and m 2 They are not identical. In the formula, M represents a rare earth ion. In the formula, X L This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents an integer of 0, 1, or 2.

[15] Optical material containing a rare earth complex (1a) as described in any one of the above items [1] to

[12] ,

[16] Furthermore, the optical material according to

[15] , comprising a resin material, inorganic glass, organic low molecular weight material or solvent,

[17] The optical material according to

[16] 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 and copolymers thereof; epoxy resin; polyimide resin; or silicon resin;

[18] The optical material according to

[16] , wherein the solvent described in

[16] is a halogenated hydrocarbon, an alcohol, an ester, a glycol ether, an ether, a ketone, or a hydrocarbon.

[19] Optical materials according to any one of the above

[16] to

[18] , which are films for solar cells, agricultural films, LED phosphors, light-emitting materials, fluorescent materials or wavelength conversion materials. That is the case. [Effects of the Invention]

[0066] The rare-earth metal complex of the present invention is an excellent wavelength conversion material that can be excited by blue light and has high acid resistance. [Brief explanation of the drawing]

[0067] [Figure 1] This is the UV-Vis· emission spectrum of the rare earth complex (1a-1) of the present invention obtained in Synthesis Example 1. [Figure 2] This is the UV-Vis emission spectrum of the rare earth complex (1a-2) of the present invention obtained in Synthesis Example 2. [Figure 3] This is the UV-Vis emission spectrum of the rare earth complex (1a-4) of the present invention obtained in Synthesis Example 4. [Figure 4] This is the UV-Vis emission spectrum of the rare earth complex (1a-5) of the present invention obtained in Synthesis Example 5. [Figure 5] This is the UV-Vis emission spectrum of the rare earth complex (1a-6) of the present invention obtained in Synthesis Example 6. [Figure 6] This is the UV-Vis emission spectrum of the rare earth complexes (1a-7) of the present invention obtained in Synthesis Example 7. [Figure 7] The UV-Vis and emission spectra of the rare earth complex (1a-8) of the present invention obtained in Synthesis Example 8. [Figure 8] The UV-Vis and emission spectra of the rare earth complex (1a-10) of the present invention obtained in Synthesis Example 10. [Figure 9] The UV-Vis and emission spectra of the rare earth complex (1a-11) of the present invention obtained in Synthesis Example 11. [Figure 10] The UV-Vis and emission spectra of the rare earth complex (1a-12) of the present invention obtained in Synthesis Example 12. [Figure 11] The UV-Vis excitation and emission spectra of the rare earth complex (1a-13) of the present invention obtained in Synthesis Example 13. [Figure 12] The UV-Vis excitation and emission spectra of the rare earth complex (1a-14) of the present invention obtained in Synthesis Example 14. [Figure 13] The UV-Vis excitation and emission spectra of the rare earth complex (1a-28) of the present invention obtained in Synthesis Example 22. [Figure 14] The UV-Vis excitation and emission spectra of the rare earth complex (1a-32) of the present invention obtained in Synthesis Example 17. [Figure 15] The UV-Vis excitation and emission spectra of the rare earth complex (1a-34) of the present invention obtained in Synthesis Example 15. [Figure 16] The UV-Vis excitation and emission spectra of the rare earth complex (1a-35) of the present invention obtained in Synthesis Example 16. [Figure 17] The UV-Vis excitation and emission spectra of the rare earth complex (1a-37) of the present invention obtained in Synthesis Example 19. [Figure 18] The UV-Vis excitation and emission spectra of the rare earth complex (1a-44) of the present invention obtained in Synthesis Example 20. [Figure 19]This is the result of single-crystal X-ray crystal structure analysis of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](1,8-bis(diphenylphosphinyl)naphthalene)europium(III)(1a-11) obtained in Synthesis Example 11. [Modes for carrying out the invention]

[0068] In the rare earth complex represented by the general formula (1a) of the present invention, R in general formula (1a) A , R B , L, m and M, R in general formula (2a) 1 , R in general formula (2b) 2 , X in general formula (3a) or general formula (3b) A , X in general formula (3b) H Furthermore, X in general formula (3c) 1 The definitions of each will be explained below.

[0069] In general formula (1a), R AThe C1-C6 haloalkyl group represented by can be linear, branched, or cyclic haloalkyl groups, including trifluoromethyl, difluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 1,1-difluoropropyl, and 1,1,1,2,3,3,3-hexafluoro-2-propyl groups. , 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, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,5-he Butafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-(1,1,2,2,2-pentafluoroethyl)propyl group, 1,2,2,3,3,4,4,4-octafluoro-1-(trifluoromethyl)butyl 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, 2,2,3,3,3-pentafluoro-1,1-bis(trifluoromethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 1,2,2,3,3,4,4,5,5,5-decafluoro-1-(trifluoromethyl)pentyl group, 1,1,2,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentyl group, 1,1,2,2,3,3,4,5,5,5-decafluoro-3-(trifluoromethyl)pentyl group, 1,1,2,2,3,3,4,5,5,5-Decafluoro-4-(trifluoromethyl)pentyl group, 2,2,3,3,4,4,4-heptafluoro-1,1-bis(trifluoromethyl)butyl group, 1,2,3,3,4,4,4-heptafluoro-1,2-bis(trifluoromethyl)butyl group, 1,2,2,3,4,4,4-heptafluoro-1,3-bis(tri(trifluoromethyl)butyl group, 1,1,3,3,4,4,4-heptafluoro-2,2-bis(tri Examples include fluoromethyl)butyl group, 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group, perfluorocyclohexyl group, perfluorocyclopentylmethyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group, etc.

[0070] The C1 group alkyl group having 1 to 3 carbon atoms may be linear, branched, or cyclic alkyl groups, and examples include methyl, ethyl, propyl, isopropyl, and cyclopropyl groups.

[0071] Examples of fluoroalkyl groups having 1 to 3 carbon atoms belonging to group T1 include linear, branched, or cyclic alkyl groups, such as trifluoromethyl, difluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 1,1-difluoropropyl, 1,1,1,2,3,3,3-hexafluoro-2-propyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, and perfluorocyclopropyl.

[0072] The alkyloxy groups having 1 to 3 carbon atoms belonging to group T1 may be linear, branched, or cyclic alkyl groups, and examples include methyloxy, ethyloxy, propyloxy, isopropyloxy, and cyclopropyloxy groups.

[0073] Examples of fluoroalkyloxy groups belonging to group T1, having 1 to 3 carbon atoms, include linear, branched, or cyclic alkyl groups, such as trifluoromethyloxy group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-difluoroethyloxy group, perfluoropropyloxy group, 2,2,3,3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1,1-difluoropropyloxy group, 1,1,1,2,3,3,3-hexafluoro-2-propyloxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, and perfluorocyclopropyloxy group.

[0074] Specifically, the aryloxy groups with 5 to 14 carbon atoms belonging to group T1 include indenyloxy, phenyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethylphenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,3,4-trimethylphenyloxy, 2,3,5-trimethylphenyloxy, and 2,3,6-trimethylphenyloxy. 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2,3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-Diethylphenyloxy group, 2-Propylphenyloxy group, 3-Propylphenyloxy group, 4-Propylphenyloxy group, 2-Isopropylphenyloxy group, 3-Isopropylphenyloxy group, 4-Isopropylphenyloxy group, 2-Cyclopropylphenyloxy group, 3-Cyclopropylphenyloxy group, 4-Cyclopropylphenyloxy group, 2-Butylphenyloxy group, 3-Butylphenyloxy group, 4-Butylphenyloxy group, 2-(1-Methylpropyl)phenyloxy group, 3-(1-Methylpropyl)phenyl Examples of substituents include hydroxyl groups, 4-(1-methylpropyl)phenyloxyl groups, 2-(2-methylpropyl)phenyloxyl groups, 3-(2-methylpropyl)phenyloxyl groups, 4-(2-methylpropyl)phenyloxyl groups, 2-cyclobutylphenyloxyl groups, 3-cyclobutylphenyloxyl groups, 4-cyclobutylphenyloxyl groups, (biphenyl-2-yl)oxyl groups, (biphenyl-3-yl)oxyl groups, (biphenyl-4-yl)oxyl groups, (phenanthrene-9-yl)oxyl groups, and (anthracene-9-yl)oxyl groups. The present invention is not limited to these exemplified substituents.

[0075] The T1 group includes monoalkylamino groups having 1 to 6 carbon atoms, which may be linear, branched, or cyclic monoalkylamino groups. Examples include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, 2-methylpropylamino group, 2,2-dimethylpropylamino group, 3-cyclopropylamino group, cyclopropylamino group, tert-butylamino group, cyclobutylamino group, pentylamino group, 2-methylpentylamino group, and hexylamino group. The present invention is not limited to these exemplified substituents.

[0076] The dialkylamino groups belonging to group T1, having 2 to 12 carbon atoms, may be linear, branched, or cyclic dialkylamino groups, including dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl)amino group, bis(2,2-dimethylpropyl)amino group, bis(3-cyclopropyl)amino group, dicyclopropylamino group, di(tert-butyl)amino group, dicyclobutylamino group, dipentylamino group, bis(2-methylpentyl)amino group, di(1-methylbutyl)amino group, bis(1,2-dimethylbutyl)amino group, di(1-ethylpropyl)amino group, dicyclopentylamino group, dihexylamino group, and dicyclo Examples of substituents include hexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propyl group, N-cyclopropyl-N-methylamino group, N-butyl-N-methylamino group, N-cyclobutyl-N-methylamino group, N-methyl-N-pentyl group, N-cyclopentyl-N-methylamino group, N-hexyl-N-methylamino group, N-cyclohexyl-N-methylamino group, N-cycloheptyl-N-methylamino group, N-methyl-N-octylamino group, N-methyl-N-nonylamino group, N-decyl-N-methylamino group, or N-methyl-N-undecylamino group, azetidyl group, pyrrolidinyl group, piperidino group, azepanyl group, morpholino group, 2-morpholinyl group, etc. The present invention is not limited to these exemplified substituents.

[0077] The monoarylamino groups with 5 to 12 carbon atoms belonging to group T1 are not particularly limited, but examples include indenylamino group, phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2,3-dimethylphenylamino group, 2,4-dimethylphenylamino group, 2,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethylphenylamino group, 2,3,4-trimethylphenylamino group, 2,3,5 -Trimethylphenylamino group, 2,3,6-trimethylphenylamino group, 2,4,5-trimethylphenylamino group, 2,4,6-trimethylphenylamino group, 3,4,5-trimethylphenylamino group, 2,3,4,5-tetramethylphenylamino group, 2,3,4,6-tetramethylphenylamino group, 2,3,5,6-tetramethylphenylamino group, 2-ethylphenylamino group, 3-ethylphenylamino group, 4-ethylphenylamino group, 2,3-diethylphenylamino group, 2,4-diethylphenylamino group 2,5-diethylphenylamino group, 2,6-diethylphenylamino group, 3,4-diethylphenylamino group, 3,5-diethylphenylamino group, 2-propylphenylamino group, 3-propylphenylamino group, 4-propylphenylamino group, 2-isopropylphenylamino group, 3-isopropylphenylamino group, 4-isopropylphenylamino group, 2-cyclopropylphenylamino group, 3-cyclopropylphenylamino group, 4-cyclopropylphenylamino group, 2-butylphenylamino group, 3- Examples of substituents include butylphenylamino group, 4-butylphenylamino group, 2-(1-methylpropyl)phenylamino group, 3-(1-methylpropyl)phenylamino group, 4-(1-methylpropyl)phenylamino group, 2-(2-methylpropyl)phenylamino group, 3-(2-methylpropyl)phenylamino group, 4-(2-methylpropyl)phenylamino group, 2-cyclobutylphenylamino group, 3-cyclobutylphenylamino group, 4-cyclobutylphenylamino group, 1-naphthylamino group, and 2-naphthylamino group. The present invention is not limited to these exemplified substituents.

[0078] Diarylamino groups with 10 to 24 carbon atoms belonging to group T1 include diindenylamine group, N-indenyl-N-phenylamino group, diphenylamino group, bis(2-methylphenyl)amino group, bis(3-methylphenyl)amino group, bis(4-methylphenyl)amino group, bis(2,3-dimethylphenyl)amino group, bis(2,4-dimethylphenyl)amino group, bis(2,5-dimethylphenyl)amino group, bis(2,6-dimethylphenyl)amino group, bis(3,4-dimethylphenyl)amino group, bis(3,5-dimethylphenyl)amino group, bis(2,3,4-trimethylphenyl)amino group, bis(2,3,5-trimethylphenyl)amino group, and bis(2,3,6-trimethylphenyl)amino group. bis(2,4,5-trimethylphenyl)amino group, bis(2,4,6-trimethylphenyl)amino group, bis(3,4,5-trimethylphenyl)amino group, bis(2,3,4,5-tetramethylphenyl)amino group, bis(2,3,4,6-tetramethylphenyl)amino group, bis(2,3,5,6-tetramethylphenyl)amino group, bis(2-ethylphenyl)amino group, bis(3-ethylphenyl)amino group, bis(4-ethylphenyl)amino group, bis(2,3-diethylphenyl)amino group, bis(2,4-diethylphenyl)amino group, bis(2,5-diethylphenyl)amino group, bis(2,6-diethylphenyl)amino group, bis(3,5-Diethylphenyl)amino group, bis(2-propylphenyl)amino group, bis(3-propylphenyl)amino group, bis(4-propylphenyl)amino group, bis(2-isopropylphenyl)amino group, bis(3-isopropylphenyl)amino group, bis(4-isopropylphenyl)amino group, bis(2-cyclopropylphenyl)amino group, bis(3-cyclopropylphenyl)amino group, bis(4-cyclopropylphenyl)amino group, bis(2-butylphenyl)amino group, bis(3-butylphenyl) Bis(4-butylphenyl)amino group, bis(4-butylphenyl)amino group, bis[2-(1-methylpropyl)phenyl]amino group, bis[3-(1-methylpropyl)phenyl]amino group, bis[4-(1-methylpropyl)phenyl]amino group, bis[2-(2-methylpropyl)phenyl]amino group, bis[3-(2-methylpropyl)phenyl]amino group, bis[4-(2-methylpropyl)phenyl]amino group, bis(2-cyclobutylphenyl)amino group, bis(3-cyclobutylphenyl)amino group, Bis(4-cyclobutylphenyl)amino group, di(1-naphthyl)amino group, di(2-naphthyl)amino group, N-(2-methylphenyl)-N-phenylamino group, N-(3-methylphenyl)-N-phenylamino group, N-(4-methylphenyl)-N-phenylamino group, N-(2,3-dimethylphenyl)-N-phenylamino group, N-(2,4-dimethylphenyl)-N-phenylamino group, N-(2,5-dimethylphenyl)-N-phenylamino group, N-(2,6-dimethylphenyl)-N- Phenylamino group, N-(3,4-dimethylphenyl)-N-phenylamino group, N-(3,5-dimethylphenyl)-N-phenylamino group, N-(2,3,4-trimethylphenyl)-N-phenylamino group, N-(2,3,5-trimethylphenyl)-N-phenylamino group, N-(2,3,6-trimethylphenyl)-N-phenylamino group, N-(2,4,5-trimethylphenyl)-N-phenylamino group, N-(2,4,6-trimethylphenyl)-N-phenylamino group, N-(3,4,Examples of substituents include 5-trimethylphenyl)-N-phenylamino groups, N-(1-naphthyl)-N-phenylamino groups, and N-(2-naphthyl)-N-phenylamino groups. The present invention is not limited to these exemplified substituents.

[0079] Diarylamino groups having 10 to 24 carbon atoms belonging to group T1 may form a ring with a nitrogen atom, and examples of such diarylamino groups having 12 to 24 carbon atoms include carbazole-9-yl group, phenothiazine-10-yl group, phenoxazine-10-yl group, 5,10-dihydrodihydrophenazine-5-yl group, 10-methyl-5,10-dihydrodihydrophenazine-5-yl group, iminostilbene-5-yl group, 9(10H)-acridon-10-yl group, 10,11-dihydro-5H-dibenzo[bf]azepine-5-yl group, and 10,11-dihydro-10-oxo-5H-dibenzo[bf]azepine-5-yl group. The present invention is not limited to these exemplified substituents.

[0080] Examples of halogen atoms belonging to group T1 include fluorine, chlorine, bromine, and iodine.

[0081] Therefore, R AThe naphthyl group represented by may be substituted with one or more substituents selected from the T1 group, specifically 1-naphthyl group, 2-naphthyl group, 1-fluoronaphthalen-2-yl group, 4-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, 1,4-difluoronaphthalen-2-yl group, 1,6-difluoronaphthalen-2-yl group, 1,4,6-trifluoronaphthalen-2-yl group, 1-methylnaphthalen-2-yl group, 4-methylnaphthalen-2-yl group, 6-methylnaphthalen-2-yl group, 3,4-dimethylnaphthalen-2-yl group, 1,6-dimethylnaphthalen-2-yl group, 1-methoxynaphthalen-2-yl group, 4-methoxynaphthalen-2-yl group, 6-methoxynaphthalen-2-yl group, 4-methoxynaphthalen-2-yl group Examples of substituents include len-1-yl group, 1,4-dimethoxynaphthalen-2-yl group, 1,6-dimethoxynaphthalen-2-yl group, 2,4-dimethoxynaphthalen-1-yl group, 6-phenoxynaphthalen-2-yl group, 4-phenoxynaphthalen-1-yl group, 1-(trifluoromethyl)naphthalen-2-yl group, 6-(trifluoromethyl)naphthalen-2-yl group, 4-(trifluoromethyl)naphthalen-2-yl group, 1-(dimethylamino)naphthalen-2-yl group, 6-(dimethylamino)naphthalen-2-yl group, 4-(dimethylamino)naphthalen-2-yl group, 1-(diphenylamino)naphthalen-2-yl group, 6-(diphenylamino)naphthalen-2-yl group, and 4-(diphenylamino)naphthalen-2-yl group. The present invention is not limited to these exemplified substituents.

[0082] Also, R A The anthryl group represented by may be substituted with one or more substituents selected from the T1 group, specifically including 9-anthryl group, 2-anthryl group, 2-fluoroanthracene-9-yl group, 2-trifluoromethylanthracene-9-yl group, 2,7-bis(trifluoromethyl)anthracene-9-yl group, 10-methylanthracene-9-yl group, and the like. The present invention is not limited to these exemplified substituents.

[0083] Furthermore, RAThe thienyl group represented by may be substituted with one or more substituents selected from the T1 group, specifically 2-thienyl group, 3-thienyl group, 3-fluorothiophen-2-yl group, 4-fluorothiophen-2-yl group, 5-fluorothiophen-2-yl group, 3,4-difluorothiophen-2-yl group, 3,5-difluorothiophen-2-yl group, 4,5-difluorothiophen-2-yl group, 3,4,5-trifluorothiophen-2-yl group, 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5-methylthiophen 3,4-dimethylthiophen-2-yl group, 3,5-dimethylthiophen-2-yl group, 4,5-dimethylthiophen-2-yl group, 3,4,5-trimethylthiophen-2-yl group, 3-ethylthiophen-2-yl group, 4-ethylthiophen-2-yl group, 5-ethylthiophen-2-yl group, 3,4-diethylthiophen-2-yl group, 3,5-diethylthiophen-2-yl group, 4,5-diethylthiophen-2-yl group, 3,4,5-triethylthiophen-2-yl group, 3-propylthiophen-2-yl group, 4-propylthiophen-2-yl group Luthiophen-2-yl group, 5-propylthiophen-2-yl group, 3,4-dipropylthiophen-2-yl group, 3,5-dipropylthiophen-2-yl group, 4,5-dipropylthiophen-2-yl group, 3,4,5-tripropylthiophen-2-yl group, 3-isopropylthiophen-2-yl group, 4-isopropylthiophen-2-yl group, 5-isopropylthiophen-2-yl group, 3,4-diisopropylthiophen-2-yl group, 3,5-diisopropylthiophen-2-yl group, 4,5-diisopropylthiophen-2-yl group, 3 ,4,5-triisopropylthiophen-2-yl group, 3-methoxythiophen-2-yl group, 4-methoxythiophen-2-yl group, 5-methoxythiophen-2-yl group, 3,4-dimethoxythiophen-2-yl group, 3,5-dimethoxythiophen-2-yl group, 4,5-dimethoxythiophen-2-yl group, 3,4,5-trimethoxythiophen-2-yl group, 3,4-ethylenedioxythiophen-2-yl group, 3-phenoxythiophen-2-yl group, 4-phenoxythiophen-2-yl group, 5-phenoxythiophen-2-yl group, 3,4-Diphenoxythiophen-2-yl group, 3,5-Diphenoxythiophen-2-yl group, 4,5-Diphenoxythiophen-2-yl group, 3,4,5-Triphenoxythiophen-2-yl group, 2-(Trifluoromethyl)thiophen-3-yl group, 3-(Trifluoromethyl)thiophen-2-yl group, 3-(Trifluoromethyl)thiophen-2-yl group, 4-(Trifluoromethyl)thiophen-2-yl group, 5-(Trifluoromethyl)thiophen-2-yl group, 3,4-Di(Trifluoromethyl) Ophen-2-yl group, 3,5-di(trifluoromethyl)thiophen-2-yl group, 4,5-di(trifluoromethyl)thiophen-2-yl group, 3,4,5-tri(trifluoromethyl)thiophen-2-yl group, 4-(trifluoromethyloxy)thiophen-2-yl group, 5-(trifluoromethyloxy)thiophen-2-yl group, 3,4-bis(trifluoromethyloxy)thiophen-2-yl group, 3,5-bis(trifluoromethyloxy)thiophen-2-yl group, 4,5-bis(trifluoromethyl) (Tyloxy)thiophen-2-yl group, 3,4,5-tris(trifluoromethyloxy)thiophen-2-yl group, 3-hydroxythiophen-2-yl group, 4-hydroxythiophen-2-yl group, 5-hydroxythiophen-2-yl group, 3,4-dihydroxythiophen-2-yl group, 3,5-dihydroxythiophen-2-yl group, 4,5-dihydroxythiophen-2-yl group, 3,4,5-trihydroxythiophen-2-yl group, 3-cyanothiophen-2-yl group, 4-cyanothiophen-2-yl group Examples of substituents include the 5-cyanothiophene-2-yl group, 3,4-dicyanothiophene-2-yl group, 3,5-dicyanothiophene-2-yl group, 4,5-dicyanothiophene-2-yl group, 3,4,5-tricyanothiophene-2-yl group, 4-nitrothiophene-2-yl group, 5-nitrothiophene-2-yl group, 3,4-dinitrothiophene-2-yl group, 3,5-dinitrothiophene-2-yl group, 4,5-dinitrothiophene-2-yl group, and 3,4,5-trinitrothiophene-2-yl group. The present invention is not limited to these exemplified substituents.

[0084] Furthermore, RAThe furanyl group represented by may be substituted with one or more substituents selected from the T1 group, specifically 2-furanyl group, 3-furanyl group, 3-fluorofuran-2-yl group, 4-fluorofuran-2-yl group, 5-fluorofuran-2-yl group, 3,4-difluorofuran-2-yl group, 3,5-difluorofuran-2-yl group, 4,5-difluorofuran-2-yl group, 3,4,5-trifluorofuran-2-yl group, 3-methylfuran-2-yl group, 4-methylfuran-2-yl group, 5-methylfuran-2-yl group, 3,4- Dimethylfuran-2-yl group, 3,5-dimethylfuran-2-yl group, 4,5-dimethylfuran-2-yl group, 3,4,5-trimethylfuran-2-yl group, 3-ethylfuran-2-yl group, 4-ethylfuran-2-yl group, 5-ethylfuran-2-yl group, 3,4-diethylfuran-2-yl group, 3,5-diethylfuran-2-yl group, 4,5-diethylfuran-2-yl group, 3,4,5-triethylfuran-2-yl group, 3-propylfuran-2-yl group, 4-propylfuran-2-yl group, 5-propylfuran-2-yl group, 3,4-dipropylfuran-2-yl group, 3,5-dipropylfuran-2-yl group, 4,5-dipropylfuran-2-yl group, 3,4,5-tripropylfuran-2-yl group, 3-isopropylfuran-2-yl group, 4-isopropylfuran-2-yl group, 5-isopropylfuran-2-yl group, 3,4-diisopropylfuran-2-yl group, 3,5-diisopropylfuran-2-yl group, 4,5-diisopropylfuran-2-yl group, 3,4,5-triisopropylfuran-2-yl group, 3-methoxyfuran-2-yl group, 5- Toxifran-2-yl group, 4-methoxyfuran-2-yl group, 5-methoxyfuran-2-yl group, 3,4-dimethoxyfuran-2-yl group, 3,5-dimethoxyfuran-2-yl group, 4,5-dimethoxyfuran-2-yl group, 3,4,5-trimethoxyfuran-2-yl group, 3-phenoxyfuran-2-yl group, 4-phenoxyfuran-2-yl group, 5-phenoxyfuran-2-yl group, 3,4-diphenoxyfuran-2-yl group, 3,5-diphenoxyfuran-2-yl group, 4,5-diphenoxyfuran-2-yl group, 3,4,5-triphenoxyfuran-2-yl group, 2-(trifluoromethyl)furan-3-yl group, 3-(trifluoromethyl)furan-2-yl group, 4-(trifluoromethyl)furan-2-yl group, 5-(trifluoromethyl)furan-2-yl group, 3,4-bis(trifluoromethyl)furan-2-yl group, 3,5-bis(trifluoromethyl)furan-2-yl group, 4,5-bis(trifluoromethyl)furan-2-yl group, 3,4,5- Tris(trifluoromethyl)furan-2-yl group, 3-(trifluoromethyloxy)furan-2-yl group, 4-(trifluoromethyloxy)furan-2-yl group, 5-(trifluoromethyloxy)furan-2-yl group, 3,4-bis(trifluoromethyloxy)furan-2-yl group, 3,5-bis(trifluoromethyloxy)furan-2-yl group, 4,5-bis(trifluoromethyloxy)furan-2-yl group, 3,4,5- ris(trifluoromethyloxy)furan-2-yl group, 3-hydroxyfuran-2-yl group, 4-hydroxyfuran-2-yl group, 5-hydroxyfuran-2-yl group, 3,4-dihydroxyfuran-2-yl group, 3,5-dihydroxyfuran-2-yl group, 4,5-dihydroxyfuran-2-yl group, 3,4,5-trihydroxyfuran-2-yl group, 3-cyanofuran-2-yl group, 4-cyanofuran-2-yl group, 5-cyanofuran Examples of substituents include -2-yl group, 3,4-dicyanofuran-2-yl group, 3,5-dicyanofuran-2-yl group, 4,5-dicyanofuran-2-yl group, 3,4,5-tricyanofuran-2-yl group, 4-nitrofuran-2-yl group, 5-nitrofuran-2-yl group, 3,4-dinitrofuran-2-yl group, 3,5-dinitrofuran-2-yl group, 4,5-dinitrofuran-2-yl group, and 3,4,5-trinitrofuran-2-yl group. The present invention is not limited to these exemplified substituents.

[0085] Next, R in general formula (2a) 1 I will explain this.

[0086] The T2 group alkyl groups having 1 to 6 carbon atoms may be linear, branched, or cyclic alkyl groups, and examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 1-methylbutyl group, 1,2-dimethylbutyl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, and cyclohexyl group. The present invention is not limited to these exemplified substituents.

[0087] Examples of alkyloxy groups having 1 to 6 carbon atoms belonging to group T2 include linear, branched, or cyclic alkyloxy groups, such as methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, 2-methylpropyloxy, 2,2-dimethylpropyloxy, 3-cyclopropylpropyloxy, cyclopropyloxy, 2-methylbutyloxy, 3-methylbutyloxy, tert-butyloxy, cyclobutyloxy, pentyloxy, 2-methylpentyloxy, 1-methylbutyloxy, 1,2-dimethylbutyloxy, 1-ethylpropyloxy, cyclopentyloxy, hexyloxy, and cyclohexyloxy. The present invention is not limited to these exemplified substituents.

[0088] As for haloalkyl groups with 1 to 6 carbon atoms belonging to group T2, R in general formula (1a) A Examples of the exemplified groups can be given as haloalkyl groups having 1 to 6 carbon atoms represented by .

[0089] The alkylcarbonyl groups having 2 to 7 carbon atoms belonging to group T2 may be linear, branched, or cyclic. Specifically, examples include acetyl group, ethyl carbonyl group, 1-propyl carbonyl group, isopropyl carbonyl group, 1-butyl carbonyl group, 2-butyl carbonyl group, tert-butyl carbonyl group, 1-pentyl carbonyl group, 2-pentyl carbonyl group, 3-pentyl carbonyl group, and 1-hexyl carbonyl group. The present invention is not limited to these exemplified substituents.

[0090] Examples of arylcarbonyl groups having 7 to 13 carbon atoms belonging to group T2 include phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, (biphenyl-2-yl)carbonyl group, (biphenyl-4-yl)carbonyl group, (4-methylphenyl)carbonyl group, and (2-methylphenyl)carbonyl group. The present invention is not limited to these exemplified substituents.

[0091] Therefore, R 1 The haloalkyl group having 1 to 6 carbon atoms represented by may be substituted with one or more substituents selected from group T2, specifically R of general formula (1a). AIn addition to the groups exemplified as C1-C6 haloalkyl groups in , other examples include 2-methoxy-1,1-difluoroethyl group, 3-methoxy-1,1-difluoropropyl group, 1,1-difluoro-2-oxopropyl group, 1,1-difluoro-2-oxobutyl group, 1,1,2,2-tetrafluoro-3-oxobutyl group, 1,1,2,2-tetrafluoro-3-oxopentyl group, 1,1,2,2,3,3-hexafluoro-4-oxopentyl group, 1,1,2,2,3,3-hexafluoro-4-oxohexyl group, 1,1-difluoro-2-oxo-3,3-dimethylbutyl group, 1,1,2,2-tetrafluoro-3-oxo-4,4-dimethylpentyl group, and 1,1-difluorobutyl group. Examples of substituents include ruolo-2-oxo-3-phenylpropyl group, 1,1-difluoro-2-oxo-3-(1-naphthyl)propyl group, 1,1-difluoro-2-oxo-3-(2-naphthyl)propyl group, 1,1,2,2-tetrafluoro-3-oxo-4-phenylbutyl group, 1,1,2,2-tetrafluoro-3-oxo-4-(1-naphthyl)butyl group, 1,1,2,2-tetrafluoro-3-oxo-4-(2-naphthyl)butyl group, 2-cyano-1,1-difluoroethyl group, 3-cyano-1,1-difluoropropyl group, 2-cyano-1,1,2,2-tetrafluoroethyl group, and 3-cyano-1,1,2,2-tetrafluoropropyl group. The present invention is not limited to these exemplified substituents.

[0092] Furthermore, R 1The aryl group having 5 to 14 carbon atoms represented by can be substituted with one or more substituents selected from the T2 group, specifically phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group Diethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-Diethylphenyl group, 2-Propylphenyl group, 3-Propylphenyl group, 4-Propylphenyl group, 2-Isopropylphenyl group, 3-Isopropylphenyl group, 4-Isopropylphenyl group, 2-Cyclopropylphenyl group, 3-Cyclopropylphenyl group, 4-Cyclopropylphenyl group, 2-Butylphenyl group, 3-Butylphenyl group, 4-Butylphenyl group, 2-(1-Methylpropyl)phenyl group, 3-(1-Methylpropyl)phenyl group, 4-(1-Methylpropyl Phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 9-anthryl group, 2-phenantrenyl group, 3-phenantrenyl group, 9-phenantrenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group , 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 2-(perfluoropropyl)phenyl group, 3-(perfluoropropyl)phenyl group, 4-(perfluoropropyl)phenyl group, 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 2-pivaloylphenyl group, 3- Examples of substituents include pivaloylphenyl group, 4-pivaloylphenyl group, 2-benzoylphenyl group, 3-benzoylphenyl group, 4-benzoylphenyl group, 2-naphthoylphenyl group, 3-naphthoylphenyl group, 4-naphthoylphenyl group, 4-methoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 4'-methoxybiphenyl-2-yl group, 4'-methoxybiphenyl-3-yl group, 4'-methoxybiphenyl-4-yl group, and 10-methoxy-9-anthryl group. The present invention is not limited to these exemplified substituents.

[0093] Furthermore, R 1The heteroaryl group having 4 to 18 carbon atoms represented by may be substituted with one or more substituents selected from the T2 group, specifically 2-furanyl group, 3-furanyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-methylpyrrol-2-yl group, 1-methylpyrrol-3-yl group, 1-phenylpyrrol-2-yl group, 1-phenylpyrrol-3-yl group, 2-benzofuranyl group, 3-bensofuranyl group, 2-benzothienyl group, 3-bensothenyl group, 1-indolyl group, 2-indolyl group, 3- Indolyl group, 1-methylindole-2-yl group, 1-methylindole-3-yl group, 1-phenylindole-2-yl group, 1-phenylindole-3-yl group, 9-methylcarbazole-2-yl group, 9-methylcarbazole-3-yl group, 9-ethylcarbazole-2-yl group, 9-ethylcarbazole-3-yl group, 9-phenylcarbazole-2-yl group, 9-phenylcarbazole-3-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, dibenzofuran-4-yl group, dibenzothiophene-2-yl group, di Benzothiophen-3-yl group, dibenzothiophen-4-yl group, 5-(trifluoromethyl)furan-2-yl group, 2-(trifluoromethyl)furan-3-yl group, 5-(trifluoromethyl)thiophen-2-yl group, 2-(trifluoromethyl)-3-thienyl group, 5-(trifluoromethyl)benzofuran-2-yl group, 6-(trifluoromethyl)benzofuran-2-yl group, 5-(trifluoromethyl)benzothiophen-2-yl group, 6-(trifluoromethyl)benzothiophen-2-yl group, 9-methyl-5-(trifluoro methyl)carbazole-2-yl group, 9-methyl-6-(trifluoromethyl)carbazole-2-yl group, 9-methyl-5-(trifluoromethyl)carbazole-3-yl group, 9-methyl-6-(trifluoromethyl)carbazole-3-yl group, 9-phenyl-5-(trifluoromethyl)carbazole-2-yl group, 9-phenyl-5-(trifluoromethyl)carbazole-3-yl group, 9-phenyl-6-(trifluoromethyl)carbazole-2-yl group, 9-phenyl-6-(trifluoromethyl)carbazole-3-yl group,Examples of substituents include 6-(trifluoromethyl)dibenzofuran-2-yl group, 7-(trifluoromethyl)dibenzofuran-2-yl group, 6-(trifluoromethyl)dibenzofuran-3-yl group, 7-(trifluoromethyl)dibenzofuran-3-yl group, 6-(trifluoromethyl)dibenzofuran-4-yl group, 7-(trifluoromethyl)dibenzofuran-4-yl group, 6-(trifluoromethyl)dibenzothiophene-2-yl group, 7-(trifluoromethyl)dibenzothiophene-2-yl group, 6-(trifluoromethyl)dibenzothiophene-3-yl group, 7-(trifluoromethyl)dibenzothiophene-3-yl group, 6-(trifluoromethyl)dibenzothiophene-4-yl group, and 7-(trifluoromethyl)dibenzothiophene-4-yl group. The present invention is not limited to these exemplified substituents.

[0094] Next, the substituent R in the optionally substituted amino group represented by general formula (Z1) Z1 and R Y1 I will explain this.

[0095] R Z1 and R Y1 Examples of C1-C6 alkyl groups represented by include the substituents listed as C1-C6 alkyl groups belonging to group T2.

[0096] R Z1 and R Y1The aryl groups with 5 to 14 carbon atoms represented by are specifically: phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, and 2,4,5-trimethylphenyl group. methylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5- Examples include diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl)phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 9-anthryl group, 2-phenantrenyl group, 3-phenantrenyl group, and 9-phenantrenyl group. The present invention is not limited to these exemplified substituents.

[0097] Examples of C1-C6 alkyl groups belonging to group T3 include the substituents exemplified as C1-C6 alkyl groups belonging to group T2.

[0098] Examples of alkyloxy groups with 1 to 6 carbon atoms belonging to group T3 include the substituents exemplified as alkyloxy groups with 1 to 6 carbon atoms belonging to group T2.

[0099] As a haloalkyl group having 1 to 6 carbon atoms belonging to the T3 group, R is a general formula (1a). A The substituents exemplified can be shown as haloalkyl groups having 1 to 6 carbon atoms represented by .

[0100] Examples of alkylcarbonyl groups with 2 to 7 carbon atoms belonging to group T3 include the substituents exemplified as alkylcarbonyl groups with 2 to 7 carbon atoms belonging to group T2.

[0101] Examples of arylcarbonyl groups with 7 to 13 carbon atoms belonging to group T3 include the substituents exemplified as alkylcarbonyl groups with 7 to 13 carbon atoms belonging to group T2.

[0102] Therefore, the optional amino group represented by general formula (Z1) may be substituted with one or more substituents selected from group T3, specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl)amino group, bis(2,2-dimethylpropyl)amino group, bis(3-cyclopropyl)amino group, dicyclopropylamino group, bis(2-methylbutyl)amino group, bis(3-methylbutyl)amino group, di(tert-butyl)amino group, dicyclobutyl Mino group, dipentylamino group, bis(2-methylpentyl)amino group, di(1-methylbutyl)amino group, bis(1,2-dimethylbutyl)amino group, di(1-ethylpropyl)amino group, dicyclopentylamino group, dihexylamino group, dicyclohexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propyl group, N-cyclopropyl-N-methylamino group, N-butyl-N-methylamino group, N-cyclobutyl-N-methylamino group, N-methyl-N-pentyl group, N-cyclopentyl-N-methylamino group, N-hexyl- Dialkyl-substituted amino groups such as N-methylamino group, N-cyclohexyl-N-methylamino group, N-cycloheptyl-N-methylamino group, N-methyl-N-octylamino group, N-methyl-N-nonylamino group, N-decyl-N-methylamino group, N-methyl-N-undecylamino group, etc., or monoalkyl-substituted amino groups such as the groups exemplified as monoalkylamino groups having 1 to 6 carbon atoms belonging to group T1, as well as (2-methoxyethyl)amino group, (2-ethoxyethyl)amino group, bis(2-methoxyethyl)amino group, bis(2-ethoxyethyl) Examples include the mino group, (2,2,2-trifluoroethyl)amino group, bis(2,2,2-trifluoroethyl)amino group, 3-chloropropylamino group, 3-bromopropylamino group, bis(3-chloropropyl)amino group, bis(3-bromopropyl)amino group, 2-bromoethylamino group, 2-chloroethylamino group, bis(2-bromoethyl)amino group, bis(2-chloroethyl)amino group, 2-cyanoethylamino group, bis(2-cyanoethyl)amino group, 3-cyanopropylamino group, and bis(3-cyanopropyl)amino group.The present invention is not limited to these exemplified substituents.

[0103] Furthermore, the optional amino group represented by general formula (Z1) may be substituted with one or more substituents selected from group T3, specifically the groups exemplified as diarylamino groups having 12 to 24 carbon atoms belonging to group T1, or indenylamino group, phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2,3-dimethylphenylamino group, 2,4-dimethylphenylamino group, 2,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethylphenylamino group, 2,3,4-trimethylphenylamino group, 2,3,5 -Trimethylphenylamino group, 2,3,6-trimethylphenylamino group, 2,4,5-trimethylphenylamino group, 2,4,6-trimethylphenylamino group, 3,4,5-trimethylphenylamino group, 2,3,4,5-tetramethylphenylamino group, 2,3,4,6-tetramethylphenylamino group, 2,3,5,6-tetramethylphenylamino group, 2-ethylphenylamino group, 3-ethylphenylamino group, 4-ethylphenylamino group, 2,3-diethylphenylamino group, 2,4-diethylphenylamino group, 2,5-diethylphenylamino group, 2,6-diethylphenylamino group, 3,4-diethylphenylamino group, 3,5-Diethylphenylamino group, 2-Propylphenylamino group, 3-Propylphenylamino group, 4-Propylphenylamino group, 2-Isopropylphenylamino group, 3-Isopropylphenylamino group, 4-Isopropylphenylamino group, 2-Cyclopropylphenylamino group, 3-Cyclopropylphenylamino group, 4-Cyclopropylphenylamino group, 2-Butylphenylamino group, 3-Butylphenylamino group, 4-Butylphenylamino group, 2-(1-Methylpropyl)phenylamino group, 3-(1-Methylpropyl)phenylamino group, 4-(1-Methylpropyl)phenylamino group, 2-(2-Methylpropyl)phenylamino group, 3-(2-Methylpropyl)phenylamino group, 4-(2-Methylpropyl)phenylamino group, 2-Cyclobutylphenylamino group, 3-Cyclobutylphenylamino group, 4-Cyclobutylphenyl Examples of substituents include monoaryl-substituted amino groups such as amino groups, 1-naphthylamino groups, and 2-naphthylamino groups, as well as (4-methoxyphenyl)amino groups, bis(4-methoxyphenyl)amino groups, (2-methoxyphenyl)amino groups, bis(2-methoxyphenyl)amino groups, [4-(trifluoromethyl)phenyl]amino groups, bis[4-(trifluoromethyl)phenyl]amino groups, (4-acetylphenyl)amino groups, bis(4-acetylphenyl)amino groups, (2-acetylphenyl)amino groups, bis(2-acetylphenyl)amino groups, (2-acetylphenyl)(4-acetylphenyl)amino groups, (4-pivaloylphenyl)amino groups, bis(4-pivaloylphenyl)amino groups, (4-benzoylphenyl)amino groups, bis(4-benzoylphenyl)amino groups, and (2-benzoylphenyl)(4-benzoylphenyl)amino groups. The present invention is not limited to these exemplified substituents.

[0104] Also, R Z1 and R Y1The substituted amino group, which forms a ring with the nitrogen atom to which it is bonded, may be substituted with one or more substituents selected from the T2 group, specifically aliphatic cyclic amino groups such as azetidyl group, pyrrolidinyl group, piperidino group, azepanyl group, morpholino group, 2-morpholinyl group, or carbazole-9-yl group, phenothiazine-10-yl group, phenoxazine-10-yl group, 5,1 Examples of cyclic amino groups include 0-dihydrodihydrophenadin-5-yl group, 10-methyl-5,10-dihydrodihydrophenadin-5-yl group, iminostylbene-5-yl group, 9(10H)-acridon-10-yl group, 10,11-dihydro-5H-dibenzo[bf]azepine-5-yl group, and 10,11-dihydro-10-oxo-5H-dibenzo[bf]azepine-5-yl group. The present invention is not limited to these exemplified substituents.

[0105] Examples of alkyl groups with 1 to 6 carbon atoms belonging to group T4 include the groups exemplified as alkyl groups with 1 to 6 carbon atoms belonging to group T2.

[0106] Examples of alkyloxy groups with 1 to 6 carbon atoms belonging to group T4 include the groups exemplified as alkyloxy groups with 1 to 6 carbon atoms belonging to group T2.

[0107] As a haloalkyl group having 1 to 6 carbon atoms belonging to the T4 group, R is a member of the general formula (1a). A Examples of the exemplified groups can be given as haloalkyl groups having 1 to 6 carbon atoms represented by .

[0108] Examples of alkylcarbonyl groups with 2 to 7 carbon atoms belonging to group T4 include the groups exemplified as alkylcarbonyl groups with 2 to 7 carbon atoms belonging to group T2.

[0109] Examples of arylcarbonyl groups with 7 to 13 carbon atoms belonging to group T4 include the groups exemplified as alkylcarbonyl groups with 7 to 13 carbon atoms belonging to group T2.

[0110] Therefore, the substituted oxy group represented by general formula (Y1) may be substituted with one or more substituents selected from group T4, specifically the groups exemplified as alkyloxy groups having 1 to 6 carbon atoms belonging to group T2, or the groups exemplified as aryloxy groups having 5 to 14 carbon atoms belonging to group T1, as well as 4-methylphenyloxy group, 3-methylphenyloxy group, 2-methylphenyloxy group, (4-methylnaphthalen-1-yl)oxy group, (6-methylnaphthalen-2-yl)oxy group, (10-methylanthracene-9-yl)oxy group, 4-Methoxyphenyl oxy group, 3-Methoxyphenyl oxy group, 2-Methoxyphenyl oxy group, (4-Methoxynaphthalen-1-yl) oxy group, (6-Methoxynaphthalen-2-yl) oxy group, (10-Methoxyanthracene-9-yl) oxy group, [4-(trifluoromethyl)phenyl] oxy group, [3-(trifluoromethyl)phenyl] oxy group, [2-(trifluoromethyl)phenyl] oxy group, [4-(trifluoromethyl)naphthalen-1-yl] oxy group, [6-(trifluoromethyl)naphthalen-2-yl] oxy group, [1 0-(trifluoromethyl)anthracene-9-yl)oxy group, 4-acetylphenyloxy group, 3-acetylphenyloxy group, 2-acetylphenyloxy group, (4-acetylnaphthalen-1-yl)oxy group, (6-acetylnaphthalen-2-yl)oxy group, (10-acetylanthracene-9-yl)oxy group, 4-pivaloylphenyloxy group, 3-pivaloylphenyloxy group, 2-pivaloylphenyloxy group, (4-pivaloylnaphthalen-1-yl)oxy group, (6-pivaloylnaphthalen-2-yl)oxy group, (10-pivaloyl (Luanthracene-9-yl)oxy group, 4-benzoylphenyloxy group, 3-benzoylphenyloxy group, 2-benzoylphenyloxy group, (4-benzoylnaphthalen-1-yl)oxy group, (6-benzoylnaphthalen-2-yl)oxy group, (10-benzoylanthracene-9-yl)oxy group, 4-cyanophenyloxy group, 3-cyanophenyloxy group, 2-cyanophenyloxy group, (4-cyanonaphthalen-1-yl)oxy group, (6-cyanonaphthalen-2-yl)oxy group, (10-cyanoanthracene-9-yl)oxy group,Examples of substituents include 4-nitrophenyloxy groups, 3-nitrophenyloxy groups, 2-nitrophenyloxy groups, (4-nitronaphthalene-1-yl)oxy groups, (6-nitronaphthalene-2-yl)oxy groups, and (10-nitroanthracene-9-yl)oxy groups. The present invention is not limited to these exemplified substituents.

[0111] Next, R in general formula (2b) 2 Let's explain the definition.

[0112] R 2 Examples of halogen atoms represented by this symbol include the halogen atoms exemplified in the section on halogen atoms belonging to group T1.

[0113] R 2 Examples of C1-C6 alkyl groups represented by include the groups listed as examples of C1-C6 alkyl groups belonging to group T2.

[0114] R 2 Examples of C2-C4 alkenyl groups represented by include vinyl group, 1-propenyl group, allyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 2-methylallyl group. The present invention is not limited to these exemplified substituents.

[0115] R 2 Examples of alkyloxy groups having 1 to 6 carbon atoms represented by this symbol include the groups listed as examples of alkyloxy groups having 1 to 6 carbon atoms belonging to group T2.

[0116] R 2 As a haloalkyl group having 1 to 6 carbon atoms represented by the general formula (1a), R A Examples of the exemplified groups can be given as haloalkyl groups having 1 to 6 carbon atoms represented by .

[0117] R 2The aryl groups with 5 to 14 carbon atoms represented by are specifically: phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, and 2,4,5-trimethylphenyl group. methylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5- Examples include diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl)phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 9-anthryl group, 2-phenantrenyl group, 3-phenantrenyl group, and 9-phenantrenyl group. The present invention is not limited to these exemplified substituents.

[0118] R 2The heteroaryl groups with 4 to 18 carbon atoms represented by include, specifically, 2-furanyl group, 3-furanyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-methylpyrrol-2-yl group, 1-methylpyrrol-3-yl group, 1-phenylpyrrol-2-yl group, 1-phenylpyrrol-3-yl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-benzothienyl group, 3-benzofuranyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 1-methylindole-2-yl group, 1-methylindole- Examples of substituents include 3-yl group, 1-phenylindole-2-yl group, 1-phenylindole-3-yl group, 9-methylcarbazole-2-yl group, 9-methylcarbazole-3-yl group, 9-ethylcarbazole-2-yl group, 9-ethylcarbazole-3-yl group, 9-phenylcarbazole-2-yl group, 9-phenylcarbazole-3-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, dibenzofuran-4-yl group, dibenzothiophene-2-yl group, dibenzothiophene-3-yl group, and dibenzothiophene-4-yl group. The present invention is not limited to these exemplified substituents.

[0119] R 2 Examples of aryloxy groups with 5 to 14 carbon atoms represented by this symbol include the groups exemplified as aryloxy groups with 5 to 14 carbon atoms belonging to group T1.

[0120] R 2 Examples of alkylcarbonyl groups having 2 to 7 carbon atoms represented by the formula include the groups exemplified as alkylcarbonyl groups having 2 to 7 carbon atoms belonging to group T2.

[0121] R 2 Examples of arylcarbonyl groups with 7 to 13 carbon atoms represented by this symbol include the groups exemplified as arylcarbonyl groups with 7 to 13 carbon atoms belonging to group T2.

[0122] In general formula (2b), two adjacent R 2The heteroaryl groups formed by the bonding of the benzene ring to which the benzene ring is attached are specifically: naphtho[2,1-b]furan-2-yl group, naphtho[2,3-b]furan-2-yl group, naphtho[1,2-b]furan-2-yl group, furo[2,3-f]-1,3-benzodioxol-6-yl group, furo[2,3-f]-1,3-benzodioxol-7-yl group, naphtho[2,1-b]thiophene-2-yl group, naphtho[2,3-b]thiophene-2-yl group, naphtho[1,2-b]thiophene-2-yl group, thieno[2,3- f)-1,3-benzodioxol-6-yl group, thieno[2,3-f]-1,3-benzodioxol-7-yl group, 3-methyl-3H-benz[e]indole-2-yl group, 3-methyl-3H-benz[e]indole-3-yl group, 3-phenyl-3H-benz[e]indole-2-yl group, 3-phenyl-3H-benz[e]indole-3-yl group, 3-acetyl-3H-benz[e]indole-2-yl group, 3-acetyl-3H-benz[e]indole-3-yl group, 1-methyl-1H-benz[f]indole 1-methyl-1H-benz[f]indole-3-yl group, 1-phenyl-1H-benz[f]indole-2-yl group, 1-phenyl-1H-benz[f]indole-3-yl group, 1-acetyl-1H-benz[f]indole-2-yl group, 1-acetyl-1H-benz[f]indole-3-yl group, 1-methyl-1H-benz[g]indole-2-yl group, 1-methyl-1H-benz[g]indole-3-yl group, 1-phenyl-1H-benz[g]indole-2-yl group, 1-phenyl-1 Examples of groups include H-benz[g]indole-3-yl group, 1-acetyl-1H-benz[g]indole-2-yl group, 1-acetyl-1H-benz[g]indole-3-yl group, 5-methyl-5H-1,3-dioxoro[4,5-f]indole-6-yl group, 5-methyl-5H-1,3-dioxoro[4,5-f]indole-7-yl group, 5-phenyl-5H-1,3-dioxoro[4,5-f]indole-6-yl group, and 5-phenyl-5H-1,3-dioxoro[4,5-f]indole-7-yl group. The present invention is not limited to these exemplified groups.

[0123] In general formula (2b), E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with C1-C6 alkyl groups such as methyl, ethyl, isopropyl, butyl, 2-methylbutyl, 3-methylbutyl, pentyl, hexyl, cyclopentyl, and cyclohexyl groups; C5-C14 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, and 4-biphenyl groups; or C2-C7 alkylcarbonyl groups such as acetyl and piperoyl groups. E is preferably an oxygen atom because it has suitable optical properties for use as an optically functional material.

[0124] R in general formula (1a) A In terms of having suitable optical properties as an optical functional material, it is preferable that the group is a fluoroalkyl group having 1 to 4 carbon atoms, an aryl group represented by general formula (2a), or a heteroaryl group represented by general formula (2b), and in terms of the absorption wavelength of the rare earth complex (1a) being extended to longer wavelengths, it is preferable that the group is an alkyloxy group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a phenoxazinyl group, a carbazoyl group, or a diphenylamino group (excluding the alkyloxy group having 1 to 4 carbon atoms; these groups are fluoroalkyl groups having 1 to 6 carbon atoms, or alkylcarbons having 2 to 5 carbon atoms). It is preferable that the group is a 2-benzofuranyl group (which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a diphenylamino group, a phenoxy group, an alkylcarbonyl group having 2 to 5 carbon atoms, a cyano group, or a nitro group), and a benzofuranyl group which may be substituted with an alkyloxy group or a nitro group having 1 to 4 carbon atoms is even more preferable in terms of ease of synthesis.

[0125] The aforementioned fluoroalkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic fluoroalkyl groups, including trifluoromethyl, difluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 1,1-difluoropropyl, and 1,1,1 Examples include 2,3,3,3-hexafluoro-2-propyl group, 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, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, and 1-methyl-3,3,3-trifluoropropyl group.

[0126] The C1-C4 alkyl group mentioned above may be linear, branched, or cyclic alkyl groups, and examples include methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, cyclopropyl, butyl, tert-butyl, and cyclobutyl groups.

[0127] The alkyloxy group having 1 to 4 carbon atoms may be linear, branched, or cyclic alkyloxy group, and examples include methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, 2-methylpropyloxy group, cyclopropyloxy group, butyloxy group, tert-butyloxy group, and cyclobutyloxy group.

[0128] Examples of the aforementioned C2-C8 dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, bis(2-methylpropyl)amino group, bis(2,2-dimethylpropyl)amino group, bis(3-cyclopropyl)amino group, dicyclopropylamino group, bis(2-methylbutyl)amino group, bis(3-methylbutyl)amino group, di(tert-butyl)amino group, dicyclobutylamino group, N-ethyl-N-methylamino group, N-methyl-N-propyl group, N-cyclopropyl-N-methylamino group, N-butyl-N-methylamino group, N-cyclobutyl-N-methylamino group, N-methyl-N-pentyl group, N-cyclopentyl-N-methylamino group, N-hexyl-N-methylamino group, N-cyclohexyl-N-methylamino group, and N-cycloheptyl-N-methylamino group.

[0129] The alkylcarbonyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic, and specific examples include acetyl group, ethylcarbonyl group, 1-propylcarbonyl group, isopropylcarbonyl group, tert-butylcarbonyl group, and the like.

[0130] Next, the R of the rare earth complex (1a) of the present invention B Let's explain the definition.

[0131] R B Examples of halogen atoms represented by this symbol include the halogen atoms exemplified in the section on halogen atoms belonging to group T1.

[0132] R B Examples of C1-C6 alkyl groups represented by include the groups exemplified in the C1-C6 alkyl groups belonging to group T2.

[0133] R B Examples of alkyloxy groups having 1 to 6 carbon atoms represented by this symbol include the groups exemplified in the T2 group's alkyloxy groups having 1 to 6 carbon atoms.

[0134] R B As an alkenyl group having 2 to 4 carbon atoms, R 2 Examples of alkenyl groups with 2 to 4 carbon atoms, as exemplified above, can be used as examples.

[0135] R B As a haloalkyl group having 1 to 6 carbon atoms, R A Examples of the groups exemplified by the haloalkyl groups having 1 to 6 carbon atoms shown above can be cited.

[0136] R B Examples of monoalkylamino groups having 1 to 6 carbon atoms represented by the formula include the groups exemplified in the T1 group monoalkylamino groups having 1 to 6 carbon atoms.

[0137] R B Examples of monoarylamino groups with 5 to 12 carbon atoms represented by this symbol include the groups exemplified in the T1 group's 5 to 12 carbon atom monoarylamino groups.

[0138] R B Examples of dialkylamino groups having 2 to 12 carbon atoms, as represented by the T1 group, include the groups exemplified in the T1 group dialkylamino groups having 2 to 12 carbon atoms.

[0139] R B Examples of diarylamino groups with 12 to 24 carbon atoms represented by this symbol include the groups exemplified in the T1 group diarylamino groups with 12 to 24 carbon atoms.

[0140] R in general formula (1a) B In terms of readily available raw materials, hydrogen atoms, chlorine atoms, bromine atoms, methyl groups, methyloxy groups, trifluoromethyl groups, and nitro groups are preferred, and hydrogen atoms are preferred in that they possess suitable optical properties for use as an optically functional material.

[0141] Next, the L of the rare earth complex (1a) of the present invention 1 and L 2 Let's explain the definition.

[0142] X in general formulas (3a) and (3b) A Let's explain the definition.

[0143] X in general formulas (3a) and (3b) A The alkyl group having 1 to 10 carbon atoms represented by can be linear, branched, or cyclic, and specifically include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2,3-dimethylcyclopropyl group, cyclobutyl group, pentyl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, Examples of substituents include cyclic secondary alkyl groups such as 4,4-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecanyl, bicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.2]octane-2-yl, and adamantane-2-yl, as well as bicyclo[2.2.1]heptan-2-yl and adamantane-1-yl. The present invention is not limited to these exemplified substituents.

[0144] Next, X in general formula (3c) 1 Let's explain the definition.

[0145] X 1 Examples of halogen atoms represented by this symbol include the halogen atoms exemplified in the section on halogen atoms belonging to group T1.

[0146] X 1 Examples of alkyl groups having 1 to 6 carbon atoms represented by this symbol include the groups exemplified in the T2 group of alkyl groups having 1 to 6 carbon atoms.

[0147] X 1 Examples of alkyloxy groups having 1 to 6 carbon atoms represented by this symbol include the alkyloxy groups having 1 to 6 carbon atoms exemplified in group T2.

[0148] X 1 As an aryl group having 5 to 14 carbon atoms, R 2 Examples of aryl groups with 5 to 14 carbon atoms, as exemplified above, can be used to illustrate this.

[0149] X 1 As a heteroaryl group having 4 to 18 carbon atoms, R 2 Examples of heteroaryl groups with 4 to 18 carbon atoms, as exemplified above, can be used to illustrate this point.

[0150] X 1 Examples of aryloxy groups having 5 to 14 carbon atoms represented by the formula include the aryloxy groups having 5 to 14 carbon atoms exemplified in group T1.

[0151] X 1 As a haloalkyl group having 1 to 6 carbon atoms, R A Examples of haloalkyl groups having 1 to 6 carbon atoms, as exemplified above, can be given.

[0152] X 1The C1-C6 haloalkyloxy group represented by may be a linear, branched, or cyclic haloalkyloxy group, including trifluoromethyloxy, difluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethyloxy, 1,1-difluoroethyloxy, 2,2-difluoroethyloxy, perfluoropropyloxy, 2,2,3,3,3-pentafluoropropyloxy, 2,2,3,3-tetrafluoropropyloxy, 3,3,3-trifluoropropyloxy, Examples include 1,1-difluoropropyloxy group, 1,1,1,2,3,3,3-hexafluoropropan-2-yloxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, perfluoropentyloxy group, perfluorocyclopentyloxy group, perfluorohexyloxy group, perfluorocyclohexyloxy group, chloromethyloxy group, bromomethyloxy group, iodomethyloxy group, 2-chloroethyloxy group, 3-bromopropyloxy group, and 3-iodopropyloxy group.

[0153] X 1If is an aryl group having 5 to 14 carbon atoms, the aryl group having 5 to 14 carbon atoms may be substituted with one or more substituents selected from the group consisting of a deuterium atom, 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. Specifically, these include deuterated phenyl group, deuterated naphthyl group, 2-methylphenyl group, 4-methylphenyl group, 2,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 2,4,6-triisopropylphenyl group, 4-tert-butylphenyl group, 1-methylnaphthalen-2-yl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 4-methylnaphthalen-2-yl group, 2-trifluoromethylphenyl group, 3-(trifluoromethyl ) Phenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, 1-(trifluoromethyl)naphthalen-2-yl group, 2-(trifluoromethyl)naphthalen-1-yl group, 4-(trifluoromethyl)naphthalen-2-yl group, 4-(trifluoromethyl)naphthalen-1-yl group, 4-methoxyphenyl group, 4-(isopropyloxy)phenyl group, 1-methoxynaphthalen-2-yl group, 2-methoxynaphthalen-1-yl group, 4-methoxynaphthalen-2-yl group, 4-trifluoromethoxyphenyl group, 1-(trifluoromethyloxy)naphthalen-2-yl group, 2-(trifluoromethyloxy)naphthalen-1-yl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,Examples of substituents include 6-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 1-bromonaphthalene-2-yl group, 2-bromonaphthalene-1-yl group, 4-bromonaphthalene-2-yl group, 6-bromonaphthalene-2-yl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 1-cyanonaphthalene-2-yl group, 2-cyanonaphthalene-1-yl group, 4-cyanonaphthalene-2-yl group, 6-cyanonaphthalene-2-yl group, 2-nitrophenyl group, 3-nitrophenyl group, and 4-nitrophenyl group. The present invention is not limited to these exemplified substituents.

[0154] X in general formula (3b) HThe alkylidene group having 1 to 10 carbon atoms represented by can be linear, branched, or cyclic, and specifically include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, methylethylene group, 2-methylpropane-1,3-diyl group, and butane-1,2-diyl group. , butane-2,3-diyl group, 2-methylpropane-2,3-diyl group, pentane-1,3-diyl group, 2-ethylpropane-1,3-diyl group, 2-methylbutane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, hexane-1,3-diyl group, 2-propylpropane-1,3-diyl group, 1-methylpentane-1,3-diyl group, 2-ethyl-butane-1,3- Diyl group, 2-methylpentane-1,3-diyl group, 2-methyl-2-ethyl-propane-1,3-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, 2-ethylbutane-1,4-diyl group, hexane-1,5-diyl group, heptane-1,5-diyl group, heptane-1,6-diyl group, octane-1,7-diyl group, nonane-1,8-diyl group, decane- Examples of substituents include 1,9-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, 1,2-cyclohexylenebis(methylene) group, 1,3-cyclohexylenebis(methylene) group, 1,4-cyclohexylenebis(methylene) group, and cycloheptitanium-1,2-diyl group. The present invention is not limited to these exemplified substituents.

[0155] X HThe C1-C10 alkenylene group represented by can be linear, branched, or cyclic, and specific examples include vinylene group, 1-methylvinylene group, propa-1-ene-1,3-diyl group, buta-1-ene-1,4-diyl group, buta-2-ene-1,4-diyl group, penta-1-ene-1,5-diyl group, penta-2-ene-1,5-diyl group, cyclopenta-1-ene-1,2-diyl group, cyclohexa-1-ene-1,2-diyl group, cycloocta-1-ene-1,2-diyl group, etc. The present invention is not limited to these exemplified substituents.

[0156] X H The alkylylene group having 1 to 10 carbon atoms represented by can be either linear or branched, and specific examples include ethynylene group, propa-1-yin-1,3-diyl group, buta-1-yin-1,3-diyl group, buta-1-yin-1,4-diyl group, buta-1,3-diyin-1,4-diyl group, penta-2-yin-1,5-diyl group, penta-2,4-diyin-1,5-diyl group, hexa-2-yin-1,6-diyl group, hexa-1,3,5-triyin-1,6-diyl group, hepta-3-yin-1,7-diyl group, octa-4-yin-1,8-diyl group, nonane-4-yin-1,9-diyl group, deca-5-yin-1,10-diyl group, etc. The present invention is not limited to these exemplified substituents.

[0157] X HThe arylene groups with 5 to 24 carbon atoms represented by the formula include, specifically, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-1,8-diyl, phenanthrene-1,2-diyl, 9,10-phenanthrene-1,2-diyl, naphthacene-1,2-diyl, naphthacene-2,3-diyl, naphthacene-1,12-diyl, naphthacene-5,6-diyl, pyrene-1,6-diyl, pyrene-1,8-diyl, pyrene-2,7-diyl, and biphenyl-2,2'-diyl. Examples of substituents include biphenyl-4,4'-diyllene 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, diphenyl ether-2,2'-diyl group, xanthene-4,5-diyl group, and 9,9-dimethylxanthene-4,5-diyl group. The present invention is not limited to these exemplified substituents.

[0158] X H Examples of heteroarylene groups having 4 to 23 carbon atoms represented by include furan-2,5-diyl group, thiophene-2,5-diyl group, benzo[b]thiophene-2,3-diyl group, benzo[1,2-b:4,5-b]dithiophene-2,6-diyl group, 9-phenylcarbazole-2,7-diyl group, 9-phenylcarbazole-3,6-diyl group, dibenzofuran-2,8-diyl group, dibenzofuran-4,6-diyl group, dibenzothiophene-2,8-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-4,6-diyl group, and 1,10-phenanthroline-3,8-diyl group. The present invention is not limited to these exemplified substituents.

[0159] L of general formula (1a)1Nitrogen-containing ligands represented by include, specifically, 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. Nanthroline, 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 Phenothroline, 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-carbonitride, 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)-2,2'-bipyridine, dimethyl-2,2'-bipyridine-4,4'-dicarboxylate, dimethyl-2,2 Examples include '-bipyridine-5,5'-dicarboxylate, diethyl-2,2'-bipyridine-4,4'-dicarboxylate, diethyl-2,2'-bipyridine-5,5'-dicarboxylate, amide compounds such as N,N-dimethylformamide; N,N-dimethylformamide-d7; N,N-dimethylacetamide, pyridine compounds such as pyridine; pyridine-d5, imidazole, 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-pyrazole-1-yl)-1,3,5-triazine-2-yl]}aniline. The present invention is not limited to these examples.

[0160] L of general formula (1a) 2Examples of neutral ligands represented by include water; heavy water; carbonyl compounds such as acetone, acetone-d6, and methyl ethyl ketone; ester compounds such as ethyl acetate and butyl acetate; alcohol compounds such as methanol, deuterium methanol, ethanol, propanol, and isopropyl alcohol; nitrile compounds such as acetonitrile, propionitrile, and acetonitrile-d3; amines such as ammonia, diethylamine, and triethylamine; ether compounds such as dimethyl ether, diethyl ether, tetrahydrofuran, tetrahydrofuran-d8, and 1,4-dioxane; and sulfur compounds such as dimethyl sulfoxide, dimethyl sulfoxide-d6, dimethyl sulfone, diphenyl sulfone, and sulfolane. The present invention is not limited to these examples.

[0161] X in the general formula (3d) 2 The C1-C4 alkyl group represented by may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, cyclopropyl, tert-butyl, and cyclobutyl groups. The present invention is not limited to these exemplified substituents.

[0162] X 2 The alkyloxy group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic, and specific examples include methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, 2-methylpropyloxy group, cyclopropyloxy group, tert-butyloxy group, and cyclobutyloxy group. The present invention is not limited to these exemplified substituents.

[0163] X 2The fluoroalkyl group having 1 to 4 carbon atoms represented by can be linear, branched, or cyclic alkyl groups, and examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2,3,3,3-hexafluoro-2-propyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, perfluorobutyl group, 4,4,4-trifluorobutyl group, 4,4,4,3,3-pentafluorobutyl group, 4,4,4,3,3,2,2-heptafluorobutyl group, and perfluorocyclobutyl group.

[0164] Also, X 2 The phenyl group represented by may be substituted with a fluorine atom, a C1-C4 alkyl group, a C1-C4 alkyloxy group, or a C1-C4 fluoroalkyl group, and more specifically, a phenyl group that may be substituted with a fluorine atom; Phenyl groups that may be substituted with C1-C4 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, cyclopropyl, tert-butyl, and cyclobutyl groups; Phenyl groups that may be substituted with C1-C4 alkyloxy groups such as methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, 2-methylpropyloxy group, cyclopropyloxy group, tert-butyloxy group, and cyclobutyloxy group; Examples include phenyl groups that may be substituted with carbon-1 to carbon-4 fluoroalkyl groups such as trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2,3,3,3-hexafluoro-2-propyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, perfluorobutyl group, 4,4,4-trifluorobutyl group, 4,4,4,3,3-pentafluorobutyl group, 4,4,4,3,3,2,2-heptafluorobutyl group, perfluorocyclobutyl group, etc.

[0165] X in the general formula (3d) 2 Preferably, the raw materials are a hydrogen atom; a C1-C4 alkyl group; a C1-C4 alkyloxy group; or a phenyl group which may be substituted with a C1-C4 alkyl group or a C1-C4 alkyloxy group, as these are readily available raw materials.

[0166] More specifically, the phosphine oxide ligands represented by general formula (3a) or general formula (3b) include triphenylphosphine oxide, cyclohexyldiphenylphosphine oxide, tri(p-tolyl)phosphine oxide, and triphenylphosphine oxide-d 15, tributylphosphine oxide, tri(tert-butyl)phosphine oxide, trioctylphosphine oxide, tricyclohexylphosphine oxide, dicyclohexylphenylphosphine oxide, dicyclohexyl(o-tolyl)phosphine oxide, 2-biphenyldicyclohexylphosphine oxide, tripentylphosphine oxide, 2-biphenyldiphenylphosphine 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(dicyclohexylphosphinyl)ethane, 1,2-Bis(diphenylphosphinyl)benzene, 1,8-Bis(diphenylphosphinyl)naphthalene, 6,6'-Bis(diphenylphosphinyl))-2,2'-bipyridine, bis[2-[(oxo)diphenylphosphino]phenyl]ether, 6,6'-Bis(diphenylphosphinyl)-1,1'-binaphthyl, 4,5-Bis(diphenylphosphinyl)-9,9-dimethylxanthene, and 4,5-Bis[di(tert-butyl)phosphinyl]-9,9-dimethylxanthene are preferred.

[0167] The 1,10-phenanthrene may be substituted with a methyl group or a phenyl group, and more specifically, 1,10-phenanthrene, 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 are preferred.

[0168] The 2,2'-bipyridine may be substituted with a methyl group or a phenyl group, and more specifically, 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 are preferred.

[0169] L in general formula (1a) 1 In terms of readily available raw materials, phosphine oxide ligands represented by general formula (3a) or general formula (3b); 1,10-phenanthrene, which may be substituted with a methyl group or a phenyl group; 2,2'-bipyridine or dipyrido[3,2-a:2',3'-c]phenazine, which may be substituted with a methyl group or a phenyl group; are preferred, and in terms of ease of synthesis, X of general formula (3a) and general formula (3b) A However, it is an alkyl group having 4 to 8 carbon atoms or an aryl group represented by the general formula (3d), X H However, it is preferable that the group is an alkylidene group having 1 to 4 carbon atoms; a diphenyl ether-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 a methyl group.

[0170] L in general formula (1a) 2 In terms of readily available raw materials, acetone, biacetone, methanol, ethanol, propanol, isopropyl alcohol, dimethyl sulfoxide, bidimethyl sulfoxide, water, or heavy water are preferred, and water is even more preferred in terms of ease of synthesis.

[0171] m in general formula (1a) 1 is an integer of 0, 1, or 2, and m 2 m is an integer, such that 0 ≤ m is 0, 1, 2, or 3. 1 +m 2 The relationship ≤ 3 is satisfied.

[0172] m in general formula (1a) 1 and m 2 In terms of having optical properties suitable for use as an optical functional material, m 1 is an integer of 1 or 2, and m 2 It is preferable that this value is 0.

[0173] Next, we will describe M of the rare earth complex (1a) of the present invention.

[0174] In general formula (1a), M represents a trivalent rare earth ion, specifically the rare earth ions of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0175] In general formula (1a), M is preferably a europium ion, a terbium ion, or a gadolinium ion due to its ease of synthesis, and more preferably a europium ion due to its suitable optical properties as an optically functional material.

[0176] Next, X of the rare earth complex (1a) of the present invention L I will explain this.

[0177] X in general formula (1a) L Examples of halide ions represented by this formula include fluoride ions, chloride ions, bromide ions, or iodide ions.

[0178] X in general formula (1a) LExamples of carboxylate ions represented by include saturated aliphatic carboxylate ions such as acetate ion, propionate ion, butyrate ion, isobutyrate ion, valerate ion, pivalate ion, or stearin ion; aromatic carboxylate ions such as benzoate ion and p-tolulate ion; unsaturated aliphatic carboxylate ions such as acrylate ion and methacrylate ion; or heteroaromatic carboxylate ions such as nicotinate ion and isonicotinate ion. The present invention is not limited to these.

[0179] X in general formula (1a) L Examples of sulfonic acid ions represented by include, specifically, organic sulfonic acid ions such as methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions, and trifluoromethanesulfonate ions; or inorganic sulfate ions such as bisulfate ions. The present invention is not limited to these.

[0180] X in general formula (1a) L Examples of sulfonic acid ions represented by include, specifically, organic sulfonic acid ions such as methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions, and trifluoromethanesulfonate ions; or bisulfate ions. The present invention is not limited to these.

[0181] X in general formula (1a) L Examples of β-diketate ions having 5 to 12 carbon atoms, represented by , include acetylacetonate ion (acac), hexafluoroacetylacetonate ion (hfa), dibenzoylmethanate ion (dbm), tenoyltrifluoroacetonate ion (tta), and 2-acetyl-5,5-dimethyl-1,3-cyclohexanedionate ion. The present invention is not limited to these.

[0182] Next, the definition of n in the rare earth complex (1a) of the present invention will be explained.

[0183] In general formula (1a), n represents an integer of 0, 1, or 2. A value of 0 is preferred for n to have suitable optical properties as an optically functional material.

[0184] Examples of rare earth complexes (1a) include structures represented by (1a-1) to (1a-126) below, but the present invention is not limited to these. In this specification, Ph represents a phenyl group, Ac represents an acetyl group, Me represents a methyl group, iPr represents an isopropyl group, Bu represents a butyl group, and tBu represents a tert-butyl group.

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193]

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[0203] [ka]

[0204] Of the above formulas (1a-1) to (1a-126), compounds represented by formulas (1a-1) to (1a-8), (1a-10) to (1a-17), (1a-28) to (1a-49), (1a-55) to (1a-63), (1a-67) to (1a-70), (1a-79) to (1a-82), (1a-84) to (1a-110), or (1a-111) are preferred in that their raw materials are readily available, and in that they are easy to synthesize, compounds represented by formulas (1a-1) to (1a-8), (1a-10) to (1a-16), (1a-22), and (1a-2 Compounds represented by formulas (5), (1a-28), (1a-31)~(1a-48), (1a-55)~(1a-63), (1a-67)~(1a-70), (1a-79)~(1a-82), (1a-84)~(1a-110) or (1a-111) are even more preferred, and formulas (1a-1), (1a-10)~(1a-11), (1a-34), (1a-37), (1a-43)~(1a-44), (1a-61)~(1a-63) or (1a-67) are particularly preferred in that they have optical properties suitable for use as optical functional materials. (Method for producing rare earth complex (1a)) Next, the method for producing the rare earth complex (1a) (hereinafter referred to as the "production method of the present invention") will be described.

[0205] (Manufacturing method 1) As a method for producing the rare earth complex (1a), an enol represented by the following general formula (4a) (hereinafter referred to as enol (4a)) and L 1 Represented by; a phosphine oxide ligand represented by the following general formula (3a); a phosphine oxide ligand represented by the following general formula (3b); or a nitrogen-containing ligand or L 2 One example of a production method is to react a neutral ligand represented by with a rare earth compound (hereinafter also referred to as Method 1).

[0206] [ka]

[0207] {where, R A R represents a C1-C6 haloalkyl group, naphthyl group, anthryl group, thienyl group, or furanyl group, and these groups, excluding the haloalkyl group, may be substituted with one or more substituents selected from the group consisting of C1-C3 alkyl groups, C1-C3 fluoroalkyl groups, C1-C3 alkyloxy groups, C1-C3 fluoroalkyloxy groups, C5-C14 aryloxy groups, C1-C6 monoalkylamino groups, C5-C12 monoarylamino groups, C2-C12 dialkylamino groups, C10-C24 diarylamino groups, methylenedioxy groups, ethylenedioxy groups, halogen atoms, hydroxyl groups, nitro groups, and cyano groups. A This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b).

[0208] [ka]

[0209] [In the formula, R 1 R represents a C1-C6 haloalkyl group, a C5-C4 aryl group, or a C4-C18 heteroaryl group, and these groups may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. 1 This represents an optionally substituted amino group shown by the following general formula (Z1).

[0210] [ka]

[0211] (In the formula, R Z1 and R Y1Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z1 and R Y1 It may form a ring together with the bonded nitrogen atom. ) Also, R 1 represents a substituted oxy group shown by the following general formula (Y1).

[0212] [ka]

[0213] (In the formula, R X1 (These are a hydrogen atom, a C1-C6 alkyl group, or a C5-C4 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups.)

[0214] [ka]

[0215] [In the formula, R 2 This represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C2-C4 alkenyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C2-C7 alkylcarbonyl group, a C7-C13 arylcarbonyl group, a cyano group, or a nitro group. Also, R 2This represents an optional amino group shown by the general formula (Z2) below.

[0216] [ka]

[0217] (In the formula, R Z2 and R Y2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z2 and R Y2 (It may also form a ring with the bonded nitrogen atom.) Multiple R 2 These may be the same or different. Also, two adjacent Rs 2 It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R B R represents a hydrogen atom, deuterium atom, halogen atom, C1-C6 alkyl group, C1-C6 alkyloxy group, C2-C4 alkenyl group, C1-C6 haloalkyl group, C1-C6 monoalkylamino group, C5-C12 monoarylamino group, C2-C12 dialkylamino group, C10-C24 diarylamino group, cyano group, or nitro group. B They may be the same or different. Also, two adjacent Rs B It may also form a ring by being integrated with the bonded benzene ring. In the formula, m 1 is an integer of 0, 1, or 2, and m 2m is an integer, such that 0 ≤ m is 0, 1, 2, or 3. 1 +m 2 The relationship ≤ 3 is satisfied. In the formula, L 1 m represents a phosphine oxide ligand or nitrogen-containing ligand represented by the following general formula (3a) or general formula (3b). 1 When L is an integer of 2, multiple L 1 They may be the same or different.

[0218] [ka]

[0219] [ka]

[0220] [In the formula, X A X represents an alkyl group having 1 to 10 carbon atoms or an aryl group represented by the following general formula (3c). A They may be the same or different.

[0221] [ka]

[0222] (In the formula, X 1 X represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C1-C6 haloalkyl group, or a C1-C6 haloalkyloxy group, and the C5-C14 aryl group may be substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkyloxy group, a hydroxyl group, a cyano group, and a nitro group. 1 (These may be the same or different.) In the formula, X HThis represents an alkylidene group with 1 to 10 carbon atoms, an alkenylene group with 1 to 10 carbon atoms, an alkynylene group with 1 to 10 carbon atoms, an arylene group with 5 to 24 carbon atoms, or a heteroarylene group with 4 to 23 carbon atoms. In the formula, L 2 m represents a neutral ligand. 2 When is an integer of 2 or 3, multiple L 2 They may be the same or different. In the formula, M represents a rare earth ion. In the formula, X L This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents an integer of 0, 1, or 2. In Method 1, R A , R B , R 1 , R 2 , E, L 1 , L 2 , M, m 1 , m 2 , n, X A , X H , X 1 and X L The definitions and specific examples shown are as follows: R in the general formulas (1a), (2a), (2b), (3a), (3b), and (3c) above. A , R B , R 1 , R 2 , E, L 1 , L 2 , M, m 1 , m 2 , n, X A , X H , X 1 and X L It is the same as this.

[0223] Phosphine oxide ligands represented by general formulas (3a) and (3b) (hereinafter referred to as phosphine oxide ligand (3a) and phosphine oxide ligand (3b)) can be obtained by methods such as those described in Chemical Reviews, Vol. 60, pp. 243-260, 1960. Commercially available products may also be used.

[0224] In Method 1, the phosphine oxide ligand (3a) used can be specifically exemplified by any of the following formulas (3a-1) to (3a-16). The present invention is not limited to these.

[0225] [ka]

[0226] In Method 1, the phosphine oxide ligand (3b) used can be specifically exemplified by any of the following formulas (3b-1) to (3b-13). The present invention is not limited to these.

[0227] [ka]

[0228] In Method 1, the nitrogen-containing ligands or neutral ligands used are specifically 1,10-phenanthrene, 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, 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine-d8, 6,6'-dimethyl-2,2'-bipyridine, and 4,4'-diphenyl-2,2' Examples include bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4',5,5'-tetramethyl-2,2'-bipyridine, water, heavy water, acetone, acetone-d6, methyl ethyl ketone, ethyl acetate, methanol, deuterium methanol, ethanol, propanol, isopropyl alcohol, acetonitrile, propionitrile, acetonitrile-d3, ammonia, diethylamine, triethylamine, diethyl ether, tetrahydrofuran, tetrahydrofuran-d8, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfoxide-d6, dimethyl sulfone, diphenyl sulfone, sulfolane, and the like. The present invention is not limited to these.

[0229] In Method 1, commercially available nitrogen-containing ligands or neutral ligands may be used.

[0230] The enol (4a) used in Method 1 can be obtained by methods described in, for example, the 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. Commercially available products may also be used.

[0231] The enol (4a) used in Method 1 loses its active proton when a base is applied to it, becoming the organic salt shown in formula (4aa) below. This organic salt (4aa) may also be used as the enol (4a), and the M'(+) shown as the countercation of the organic salt (4aa) in this case can be exemplified by alkali metal ions such as lithium ions, sodium ions, potassium ions, and cesium ions; 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. The present invention is not limited to these.

[0232] [ka]

[0233] Examples of rare earth compounds used in Method 1 include, as europium compounds, halide salts or hydrates thereof such as europium(III) fluoride, europium(III) chloride, europium(III) bromide, and europium(III) iodide; organic salts or hydrates thereof such as europium(III) oxalate, europium(III) acetate, europium(III) trifluoroacetate, and europium(III) trifluoromethanesulfonic acid; metal alkoxides such as tris[N,N-bis(trimethylsilyl)amide] europium(III), europium(III) trimethoxide, europium(III) triethoxide, and europium(III) tri(isopropoxide); or inorganic salts or hydrates thereof such as europium(III) phosphate, europium(III) sulfate, and europium(III) nitrate. In particular, inorganic salts such as europium(III) chloride and europium(III) nitrate or their hydrates are preferred in terms of good reaction yield; or organic salts such as europium(III) oxalate, europium(III) acetate, europium(III) trifluoroacetate, and europium(III) trifluoromethanesulfonic acid or their hydrates are preferred, and europium(III) acetate, europium(III) chloride, or europium(III) nitrate or their hydrates are even more preferred.

[0234] The rare earth compounds used in Method 1 can be commercially available products.

[0235] In Method 1, L 1 or / and L 2The rare earth compounds used may include, specifically, inorganic salt hydrates such as europium acetate n-hydrate, europium nitrate pentahydrate, europium chloride hexahydrate, and complex compounds such as bis(triphenylphosphine oxide) europium(III) chloride, bis(tricyclohexylphosphine oxide) europium(III) chloride, bis[tri(o-tolyl)phosphine oxide] europium(III) chloride, tris(triphenylphosphine oxide) europium(III) chloride, bis(triphenylphosphine oxide) europium(III) nitrate, bis(triphenylphosphine oxide) europium(III) acetate, (phenanthrene) europium(III) chloride, bis(phenanthrene) europium(III) chloride, and (bipyridine) europium(III) chloride. The present invention is not limited to these exemplified compounds. Among these, inorganic salt hydrates such as europium acetate n-hydrate, europium nitrate pentahydrate, and europium chloride hexahydrate are preferred because the raw materials are readily available. These complex compounds can be obtained by methods such as those described in RSC Advances, Vol. 6, pp. 90934-90943, 2016. Commercially available products may also be used.

[0236] In Method 1, it is preferable to carry out the reaction in a solvent because it yields a good amount of the rare earth complex (1a). There are no particular restrictions on the type of solvent that can be used, as long as it does not inhibit the reaction. Examples of usable solvents 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; or water. These solvents can be used individually or in any mixture of two or more in any ratio. Dichloromethane, chloroform, methylcyclohexane, acetone, methanol, ethanol, or water are preferred as solvents because they yield a good reaction yield of the rare earth complex (1a).

[0237] The molar ratio of the rare earth compound and enol(4a) in Method 1 will be explained. It is preferable to use 1.0 to 5.0 moles of enol(4a) per mole of rare earth compound, and more preferably 3.0 to 4.0 moles of enol(4a).

[0238] In Method 1, L 1 When phosphine oxide ligand (3a) is used, the molar ratio of the rare earth compound and phosphine oxide ligand (3a) will be explained. It is preferable to use 0.5 to 5.0 moles of phosphine oxide ligand (3a) per mole of rare earth compound, and more preferably 1.0 to 3.0 moles of phosphine oxide ligand (3a).

[0239] In Method 1, L 1 When phosphine oxide ligand (3b) is used, the molar ratio of the rare earth compound and phosphine oxide ligand (3b) will be explained. It is preferable to use 0.5 to 2.5 moles of phosphine oxide ligand (3b) per mole of rare earth compound, and more preferably 1.0 to 1.5 moles of phosphine oxide ligand (3b).

[0240] In Method 1, L 1 When a nitrogen-containing ligand is used, the molar ratio of the rare earth compound to the nitrogen-containing ligand will be explained. It is preferable to use 0.5 to 2.5 moles of nitrogen-containing ligand per mole of rare earth compound, and more preferably 1.0 to 1.5 moles of nitrogen-containing ligand.

[0241] The molar ratio of the rare earth compound and the neutral ligand in Method 1 will be explained. It is preferable to use 0.5 to 10 moles of neutral ligand per mole of rare earth compound, and more preferably 1.0 to 8.0 moles of neutral ligand.

[0242] In Method 1, a base may be added to accelerate the reaction. Examples of such bases include organic amines such as trimethylamine, triethylamine, diethylamine, pyridine, and quinoline; or inorganic bases such as sodium carbonate, potassium carbonate, or other carbonates; sodium bicarbonate, potassium bicarbonate, or other bicarbonates; sodium hydroxide, potassium hydroxide, lithium hydroxide, or other hydroxides; or ammonia. Preferably, the equivalent amount of the base used is 1.0 to 10 moles per mole of enol(4a), more preferably 2.0 to 8.0 moles, and even more preferably 3.0 to 5.0 moles.

[0243] In Method 1, there are no particular restrictions on the reaction temperature and reaction time, and general conditions used by those skilled in the art for producing metal complexes can be used. Specifically, rare earth complex (1a) can be produced in good yield by selecting a reaction time of 1 minute to 120 hours at a reaction temperature of -80°C to 120°C.

[0244] The rare earth complex (1a) produced by Method 1 can be purified by appropriately selecting and using a general purification method used by those skilled in the art to purify metal complexes. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, and column chromatography.

[0245] (Manufacturing method 2) As a method for producing the rare earth complex (1a) of the present invention, a diketonate complex represented by the following general formula (1aq) and L 1 Represented by; a phosphine oxide ligand represented by the following general formula (3a); a phosphine oxide ligand represented by the following general formula (3b); or a nitrogen-containing ligand or L 2 Another method for producing the rare earth complex (1a), characterized by reacting it with a neutral ligand represented by , can also be mentioned (hereinafter also referred to as Method 2).

[0246] [ka]

[0247] {where, R AR represents a C1-C6 haloalkyl group, naphthyl group, anthryl group, thienyl group, or furanyl group, and these groups, excluding the haloalkyl group, may be substituted with one or more substituents selected from the group consisting of C1-C3 alkyl groups, C1-C3 fluoroalkyl groups, C1-C3 alkyloxy groups, C1-C3 fluoroalkyloxy groups, C5-C14 aryloxy groups, C1-C6 monoalkylamino groups, C5-C12 monoarylamino groups, C2-C12 dialkylamino groups, C10-C24 diarylamino groups, methylenedioxy groups, ethylenedioxy groups, halogen atoms, hydroxyl groups, nitro groups, and cyano groups. A This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b).

[0248] [ka]

[0249] (In the formula, R 1 R represents a C1-C6 haloalkyl group, a C5-C4 aryl group, or a C4-C18 heteroaryl group, and these groups may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. 1 This represents an optionally substituted amino group shown by the following general formula (Z1).

[0250] [ka]

[0251] (In the formula, R Z1 and R Y1Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z1 and R Y1 It may form a ring together with the bonded nitrogen atom. ) Also, R 1 represents a substituted oxy group shown by the following general formula (Y1).

[0252] [ka]

[0253] (In the formula, R X1 (These are a hydrogen atom, a C1-C6 alkyl group, or a C5-C4 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups.)

[0254] [ka]

[0255] [In the formula, R 2 This represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C2-C4 alkenyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C2-C7 alkylcarbonyl group, a C7-C13 arylcarbonyl group, a cyano group, or a nitro group. Also, R 2This represents an optional amino group shown by the general formula (Z2) below.

[0256] [ka]

[0257] (In the formula, R Z2 and R Y2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C5-C14 aryl group, and the alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkyloxy groups, C1-C6 haloalkyl groups, C2-C7 alkylcarbonyl groups, C7-C13 arylcarbonyl groups, cyano groups, and nitro groups. Z2 and R Y2 (It may also form a ring with the bonded nitrogen atom.) Multiple R 2 These may be the same or different. Also, two adjacent Rs 2 It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or an alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R B R represents a hydrogen atom, deuterium atom, halogen atom, C1-C6 alkyl group, C1-C6 alkyloxy group, C2-C4 alkenyl group, C1-C6 haloalkyl group, C1-C6 monoalkylamino group, C5-C12 monoarylamino group, C2-C12 dialkylamino group, C10-C24 diarylamino group, cyano group, or nitro group. B They may be the same or different. Also, two adjacent Rs B It may also form a ring by being integrated with the bonded benzene ring. In the formula, m 1 is an integer of 0, 1, or 2, and m 2m is an integer, such that 0 ≤ m is 0, 1, 2, or 3. 1 +m 2 The relationship ≤ 3 is satisfied. In the formula, L 1 m represents a phosphine oxide ligand or nitrogen-containing ligand represented by the following general formula (3a) or general formula (3b). 1 When L is an integer of 2, multiple L 1 They may be the same or different.

[0258] [ka]

[0259] [ka]

[0260] [In the formula, X A X represents an alkyl group having 1 to 10 carbon atoms or an aryl group represented by the following general formula (3c). A They may be the same or different.

[0261] [ka]

[0262] (In the formula, X 1 X represents a hydrogen atom, a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C5-C14 aryl group, a C4-C18 heteroaryl group, a C5-C14 aryloxy group, a C1-C6 haloalkyl group, or a C1-C6 haloalkyloxy group, and the C5-C14 aryl group may be substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkyloxy group, a hydroxyl group, a cyano group, and a nitro group. 1 (These may be the same or different.) In the formula, X HThis represents an alkylidene group with 1 to 10 carbon atoms, an alkenylene group with 1 to 10 carbon atoms, an alkynylene group with 1 to 10 carbon atoms, an arylene group with 5 to 24 carbon atoms, or a heteroarylene group with 4 to 23 carbon atoms. In the formula, L 2 m represents a neutral ligand. 2 When is an integer of 2 or 3, multiple L 2 They may be the same or different. In the formula, m represents an integer of 0, 1, 2, or 3. In the formula, Q 1 represents a neutral molecule. However, m 1 When Q is 0, 1 and L 2 They are identical and m and m 2 They are not identical. In the formula, M represents a rare earth ion. In the formula, X L This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents an integer of 0, 1, or 2. In Method 2, R A , R B , R 1 , R 2 , E, L 1 , L 2 , M, m 1 , m 2 , n, X A , X H , X 1 and X L The definitions and specific examples shown are as follows: R in the general formulas (1a), (2a), (2b), (3a), (3b), and (3c) above. A , R B , R 1 , R 2 , E, L 1 , L 2 , M, m 1 , m 2 , n, X A , X H , X 1 and X L It is the same as this.

[0263] In Method 2, Q 1 Examples of neutral molecules represented by 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. The present invention is not limited to these.

[0264] The diketonate complex (1aq) used in Method 2 can be obtained by methods described in the Journal of the American Chemical Society, Vol. 87, pp. 5254-5256, 1965, etc.

[0265] Specific examples of the diketonate complex (1aq) used in Method 2 include structures represented by any of the following (1aq-1) to (1aq-72). The present invention is not limited to these.

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] [ka]

[0271] [ka]

[0272] [ka]

[0273] [ka]

[0274] [ka]

[0275] [ka]

[0276] [ka]

[0277] [ka]

[0278] L in Method 2 1 However, when it is a phosphine oxide ligand (3a) or a phosphine oxide ligand (3b), it can be obtained by the method exemplified in the description of Method 1 above. Alternatively, commercially available products can also be used.

[0279] In Method 2, L 1 If the phosphine oxide (3a) is used, the phosphine oxide (3a) used can be the same as that exemplified in the description of Method 1 above.

[0280] In Method 2, L 1 If the phosphine oxide (3b) is used, the phosphine oxide (3b) used can be the same as that exemplified in the description of Method 1 above.

[0281] In Method 2, L 1 If the ligand is nitrogen-containing, the example of the nitrogen-containing ligand used can be the same as that exemplified in the description of Method 1 above.

[0282] Examples of neutral ligands used in Method 2 are the same as those exemplified in the description of Method 1 above.

[0283] In Method 2, it is preferable to carry out the reaction in a solvent because it yields a good amount of the rare earth complex (1a). There are no particular restrictions on the type of solvent that can be used, as long as it does not inhibit the reaction. Examples of usable solvents 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; or water. These solvents can be used individually or in any ratio of two or more. Dichloromethane, chloroform, acetone, methylcyclohexane, methanol, ethanol, or water are preferred solvents due to their good yield of the rare earth complex (1a).

[0284] In Method 2, L1 When the phosphine oxide ligand (3a) is used, the molar ratio of the diketonate complex (1aq) and the phosphine oxide ligand (3a) will be explained. It is preferable to use 0.5 to 5.0 moles of the phosphine oxide ligand (3a) per mole of the diketonate complex (1aq), and more preferably 1.0 to 3.0 moles of the phosphine oxide ligand (3a).

[0285] In Method 2, L 1 When the phosphine oxide ligand (3b) is used, the molar ratio of the diketonate complex (1aq) and the phosphine oxide ligand (3b) will be explained. It is preferable to use 0.5 to 2.5 moles of the phosphine oxide ligand (3b) per mole of the diketonate complex (1aq), and more preferably 1.0 to 1.5 moles of the phosphine oxide ligand (3b).

[0286] In Method 2, L 1 When a nitrogen-containing ligand is used, the molar ratio of the diketonate complex (1 aq) to the nitrogen-containing ligand will be explained. It is preferable to use 0.5 to 2.5 moles of nitrogen-containing ligand per mole of diketonate complex (1 aq), and more preferably 1.0 to 1.5 moles of nitrogen-containing ligand.

[0287] The molar ratio of the diketonate complex (1 aq) and the neutral ligand in Method 2 will be explained. It is preferable to use 0.5 to 10 moles of neutral ligand per mole of diketonate complex (1 aq), and more preferably 1.0 to 8.0 moles of neutral ligand.

[0288] Furthermore, in Method 2, there are no particular restrictions on the reaction temperature and reaction time, and general conditions used by those skilled in the art for producing metal complexes can be used. Specifically, by selecting a reaction temperature of -80°C to 120°C and a reaction time of 1 minute to 120 hours, rare earth complex (1a) can be produced in a high reaction yield.

[0289] The rare earth complex (1a) produced by Method 2 can be purified by appropriately selecting and using a general purification method used by those skilled in the art to purify metal complexes. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, and column chromatography.

[0290] Enol (4a) can undergo isomerization to form enol (4ai) or β-diketone (4aii). The present invention encompasses all of enol (4a), enol (4ai), and β-diketone (4aii), but for convenience, these isomers are denoted as general formula (4a) in this specification. Similarly, rare earth complex (1a) can undergo isomerization to form rare earth complex (1ai), but rare earth complex (1a) includes rare earth complex (1ai). In this specification, rare earth complex (1ai) is also denoted as general formula (1a). Furthermore, diketonate complex (1aqi) undergoes isomerization in the same way as rare earth complex (1a). In this specification, diketonate complex (1aqi) is also denoted as general formula (1aq).

[0291] [ka]

[0292] (In the formula, R A and R B R in the general formula (1a) is A and R B (This expresses the same meaning.)

[0293] [ka]

[0294] (In the formula, R A , R B , L 1 , L 2 , M, m 1 , m 2 , n and X L R in the general formula (1a) is A , RB , L 1 , L 2 , M, m 1 , m 2 , n and X L (This expresses the same meaning.)

[0295] [ka]

[0296] (In the formula, R A , R B M, X L m and n are R in the general formula (1aq) above. A , R B L, M, X L , m, n and Q 1 (This expresses the same meaning.) The rare earth complex (1a) of the present invention is excitable with blue light and has high acid resistance. Therefore, it is useful as an optical material containing the rare earth complex (1a), and such optical materials are particularly useful as light-emitting materials such as films for solar cells, agricultural films, LED phosphors, and security inks, as well as wavelength conversion materials used in them.

[0297] Furthermore, the rare earth complex (1a) of the present invention can be used as an optical material containing one or more selected from resin materials, inorganic glass, and organic low molecular weight materials, and is particularly preferable to use an optical material containing a resin material due to its high dispersibility. Examples of the resin material include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, and other polymethacrylates, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl methacrylate, polyisobutyl acrylate, and polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, and polyisobutyl acrylate. Examples include polyacrylates such as polytert-butyl acrylate, fluorinated polymethyl acrylate, fluorinated polyethyl acrylate, fluorinated polypropyl acrylate, fluorinated polyisopropyl acrylate, fluorinated polybutyl acrylate, fluorinated polysec-butyl acrylate, fluorinated polyisobutyl acrylate, and fluorinated polytert-butyl acrylate; polyolefins such as polystyrene, polyethylene, polypropylene, polybutene, fluorinated polyethylene, fluorinated polypropylene, and fluorinated polybutene; polyvinyl ether, fluorinated polyvinyl ether, polyvinyl acetate, polyvinyl chloride, or copolymers thereof; cellulose; polyacetal; polyester; polycarbonate; epoxy resin; polyamide resin; polyimide resin; polyurethane; Nafion; petroleum resin; rosin; and silicon resin.

[0298] Among these, 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 resin; polyimide resin; silicon resin, etc. are particularly preferred. These may be used individually or in combination of two or more.

[0299] The content of the europium complex (1a) in the optical material containing the rare earth complex (1a) and a resin material of the present invention is preferably 0.001 to 99% by weight, and more preferably 0.01 to 50% by weight.

[0300] Inorganic glass can be any type commonly used by those skilled in the art, such as soda-lime glass, crystal glass, or borosilicate glass.

[0301] The organic low molecular weight material can be any material commonly used by those skilled in the art, such as ionic liquids like amyltriethylammonium bis(trifluoromethanesulfonyl)imide and tetraamylammonium chloride; or hydrocarbons such as pentadecane, hexadecane, octadecane, nonadecane, eicosane, and paraffin.

[0302] Methods for obtaining an optical material containing the rare earth complex (1a) of the present invention include: using the rare earth complex (1a) alone to make an optical material; incorporating the rare earth complex (1a) into an optical material containing one or more selected from a resin material, inorganic glass, and organic low molecular weight material to make an optical material; mixing the rare earth complex (1a) with a corresponding monomer when polymerizing the resin material and polymerizing the monomer to make an optical material; and dissolving and dispersing the rare earth complex (1a) in a solvent to make an optical material.

[0303] When the rare earth complex (1a) of the present invention is dissolved and dispersed in a solvent to form an optical material, suitable solvents include, for example, 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; or water. These solvents can be used individually or mixed in any ratio of two or more types.

[0304] Among these, halogenated hydrocarbons, alcohols, esters, glycol ethers, ethers, ketones, or hydrocarbons are preferred. [Examples]

[0305] The present invention will be described in more detail below with reference to synthesis examples, comparative examples, and evaluation examples, but the present invention is not limited to these.

[0306] The following analytical methods were used to identify the rare earth complex (1a).

[0307] 1 H-NMR, 19 F-NMR and 31 For P-NMR measurements, we used BRUKER's ULTRASHIELD PLUS AVANCE III (400MHz, 376MHz, and 162MHz) and ASCEND AVANCE III HD (400MHz, 376MHz, and 162MHz). 1 ¹H-NMR was measured using deuterated chloroform (CDCl3) as the measurement solvent and tetramethylsilane (TMS) as the internal standard. 19 F-NMR was measured using deuterated chloroform (CDCl3), deuterated acetone (Acetone-d6), and deuterated dimethyl sulfoxide (DMSO-d6) as the measurement solvents. 31 P-NMR was measured using deuterated chloroform (CDCl3).

[0308] Mass spectrometry measurements were performed using a Waters 2695-micromass ZQ4000 from Waters Inc.

[0309] Excitation and emission spectra were measured using a spectrophotometer (JASCO Corporation, FP-6500).

[0310] The UV-Vis spectrum was measured using an ultraviolet-visible-near-infrared spectrophotometer (JASCO Corporation, V-670).

[0311] The emission quantum yield was measured using absolute PL quantum yield analyzers (Hamamatsu Photonics, C9920-03 and C11347-01).

[0312] For single-crystal X-ray crystal structure analysis, the obtained single crystals were mounted on a goniometer head and measured using a Rigaku XtaLAB Synergy instrument. Details of the analysis conditions are shown below.

[0313] <Analysis conditions> X-ray source: CuKα (λ=1.54184Å) Detector: Single-photon detection hybrid pixel detector Furthermore, commercially available reagents were used. (Reference example 1)

[0314] [ka]

[0315] Benzofuran-2-carboxylic acid (6.53 g, 40.3 mmol) and N,N-dimethyl-4-aminopyridine (4.92 g, 40.3 mmol) were dissolved in N,N-dimethylformamide (244 mL) and stirred at room temperature for 5 minutes. To this solution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (7.73 g, 40.3 mmol) was added and stirred at room temperature for 5 minutes, then 1,3-indanedione (1.97 g, 13.4 mmol) was added and stirred at room temperature for 70 hours. The reaction mixture was cooled to 0°C, and 2M hydrochloric acid (448 mL) cooled on ice was added. The precipitated solid was filtered and washed with 2M hydrochloric acid (403 mL) cooled on ice and water (403 mL). The obtained solid was dried under reduced pressure, dispersed in 1M sodium hydroxide (268 mL), and sonicated for 20 minutes. Dichloromethane (349 mL) was added, and after sonication for 20 minutes, the solid was filtered and washed with dichloromethane. The obtained solid was dried under reduced pressure, dissolved in 2M hydrochloric acid (269 mL) and dichloromethane (269 mL), and after liquid-liquid separation, the aqueous layer was extracted with dichloromethane (269 mL). The organic layer was combined and concentrated under reduced pressure, and the resulting crude was reprecipitated with chloroform / hexane to obtain a brown solid of 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 2.53 g, yield 65%). Furthermore, the mother liquor of the recrystallized product was concentrated under reduced pressure, dried, and the resulting crude product was reprecipitated again with chloroform / hexane to obtain a brown solid of 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 610 mg, yield 16%, total yield of the target product obtained from the two reprecipitations 3.14 g, total yield 81%). 1H-NMR (400MHz, CDCl3) δ (ppm): 15.38 (brs, 1H), 9.31 (brs, 1H), 7.92-7.70 (m, 5H), 7.65 (dd, J=8.4, 1.0Hz, 1H), 7.56-7.51 (m, 1H), 7.39-7.31 (m, 1H). (Reference example 2)

[0316] [ka]

[0317] 7-Methoxybenzofuran-2-carboxylic acid (5.31 g, 27.6 mmol) and N,N-dimethyl-4-aminopyridine (3.37 g, 27.6 mmol) were dissolved in N,N-dimethylformamide (167 mL) and stirred at room temperature for 5 minutes. To this solution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (5.29 g, 27.6 mmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (1.34 g, 9.20 mmol) was added and the mixture was stirred at room temperature for 118 hours. The reaction mixture was cooled to 0°C, and 2M hydrochloric acid (370 mL) cooled on ice was added. The precipitated solid was filtered and washed with 2M hydrochloric acid (279 mL) cooled on ice and water (279 mL). After drying the obtained solid under reduced pressure, it was dispersed in 250 mL of 1M aqueous sodium hydroxide solution and irradiated with sonication for 20 minutes. Dichloromethane (250 mL) was added, and after sonication for 20 minutes, the solid was filtered and washed with dichloromethane. The obtained solid was dried under reduced pressure, dissolved in 2M hydrochloric acid (250 mL) and dichloromethane (200 mL), and after liquid-liquid separation, the aqueous layer was extracted with dichloromethane (250 mL x 2). The organic layer was combined, concentrated under reduced pressure, and washed with hexane to obtain a yellow solid of 2-(7-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 2.31 g, yield 79%). 1H-NMR(400MHz,CDCl3)δ(ppm):15.24(brs,1H),9.26(s,1H),7.93-7.83(m,2H),7.80-7.69(m,2H ),7.37(dd,J=7.9,0.8Hz,1H),7.27(dd,J=7.9,7.9Hz,1H),6.99(brd,J=7.9Hz,1H),4.05(s,3H). (Reference example 3)

[0318] [ka]

[0319] Methyl 6-methoxybenzofuran-2-carboxylate (1.02 g, 4.94 mmol) was dissolved in tetrahydrofuran (5.5 mL), methanol (5.5 mL), and water (5.5 mL). Lithium hydroxide monohydrate (415 mg, 9.90 mmol) was added, and the mixture was stirred at room temperature for 24 hours. 1 M hydrochloric acid (6.0 mL) was added to the reaction mixture, the precipitated solid was filtered, washed with water, and then recrystallized with ethanol / hexane. The precipitated solid was filtered and dried by heating to obtain a white solid of 6-methoxybenzofuran-2-carboxylic acid (yield 736 mg, yield 78%). 1 H-NMR (400MHz, CDCl3) δ7.63(d,J=0.7Hz,1H),7.57(d,J=8.7Hz,1H),7.08(d,J=1.9Hz,1H),6.97(dd,J=8.7,2.2Hz,1H),3.89(s,3H).

[0320] 6-Methoxybenzofuran-2-carboxylic acid (736 mg, 3.80 mmol) and N,N-diisopropylethylamine (2.0 mL, 12 mmol) were dissolved in N,N-dimethylformamide (60 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (1.75 g, 4.56 mmol) was added and stirred at room temperature for 5 minutes, then 1,3-indanedione (1.68 g, 11.5 mmol) was added and stirred at room temperature for 22 hours. The reaction mixture was cooled to 0°C, and 120 mL of ice-cold 2M hydrochloric acid was added. The precipitated solid was filtered off and washed with 100 mL of ice-cold 2M hydrochloric acid and 100 mL of water. The obtained solid was dried under reduced pressure, dispersed in 1M sodium hydroxide aqueous solution (80 mL), and sonicated for 10 minutes. Dichloromethane (80 mL) was added, and sonication was irradiated for 10 minutes. The solid was then filtered and washed with dichloromethane. The obtained solid was dissolved in 2M hydrochloric acid (80 mL) and dichloromethane (80 mL), and after liquid-liquid extraction, the aqueous layer was extracted with dichloromethane (80 mL x 3). The organic and aqueous layers were combined, dried over sodium sulfate, concentrated under reduced pressure, and washed with acetone. The obtained crude product was reprecipitated with chloroform / hexane to obtain a yellow solid of 2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 612 mg, yield 50%). 1 H-NMR(400MHz,CDCl3)δ15.3(brs,1H),9.30(d,J=1.0Hz,1H),7.89-7.83(m,2H),7.45(dt,J=7.0,1.5Hz,1H),7.7 0(dt,J=7.0,1.5Hz,1H),7.66(d,J=8.7Hz,1H),7.10(brd,J=1.8Hz,1H),7.00(dd,J=8.8,2.3Hz,1H),3.90(s,3H). (Reference example 4)

[0321] [ka]

[0322] 5-Methoxybenzofuran-2-carboxylic acid (769 mg, 4.00 mmol) and N,N-diisopropylethylamine (2.09 mL, 12.0 mmol) were dissolved in N,N-dimethylformamide (80 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (1.83 g, 4.80 mmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (1.75 g, 12.0 mmol) was added and stirred at room temperature for 3 days. The reaction mixture was cooled to 0°C, and 2M hydrochloric acid (160 mL) cooled on ice was added. The precipitated solid was filtered off and washed with 2M cold hydrochloric acid (100 mL) and water (100 mL). The obtained solid was reprecipitated with chloroform / hexane, and the precipitated solid was washed twice with acetone to obtain a yellow solid of 2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 483 mg, yield 38%). 1 H-NMR(400MHz,CDCl3)δ15.3(brs,1H),9.24(brs,1H),7.89(brd,J=7.1Hz,1H),7.87(brd,J=7.1Hz,1H),7.77( dt,J=7.4,1.2Hz,1H),7.72(dt,J=7.4Hz,1.2Hz,1H),7.54(brd,J=8.6Hz,1H),7.18-7.14(m,2H),3.89(s,3H). (Reference example 5)

[0323] [ka]

[0324] Ethyl 5-nitrobenzofuran-2-carboxylate (9.41 g, 40.0 mmol) was dissolved in tetrahydrofuran (51 mL), methanol (51 mL), and water (51 mL). Lithium hydroxide monohydrate (3.36 g, 80 mmol) was added, and the mixture was stirred at room temperature for 21 hours. 1 M hydrochloric acid (80 mL) was added to the reaction mixture, and the precipitated solid was filtered off, washed with water, and then heated and dried to obtain a yellowish-white solid of 5-nitrobenzofuran-2-carboxylic acid (yield 7.58 g, yield 92%).1 H-NMR (400MHz, DMSO) δ (ppm): 8.77 (d, J = 2.2 Hz, 1H), 8.36 (dd, J = 9.1, 2.3 Hz, 1H), 7.97 (d, J = 9.2 Hz, 1H), 7.86 (s, 1H).

[0325] 5-nitrobenzofuran-2-carboxylic acid (3.73 g, 18.0 mmol) and N,N-dimethyl-4-aminopyridine (2.20 g, 18.0 mmol) were dissolved in N,N-dimethylformamide (109 mL) and stirred at room temperature for 5 minutes. To this solution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (3.45 g, 18.0 mmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (877 mg, 6.00 mmol) was added and the mixture was stirred at room temperature for 120 hours. 225 mL of 2M hydrochloric acid (cooled to 0°C) was added to the reaction mixture, and the precipitated solid was filtered off and washed with 173 mL of 2M hydrochloric acid (cooled to 0°C) and water (173 mL). The resulting solid was dried under reduced pressure, and sonication was performed with 116 mL of 1M aqueous sodium hydroxide solution for 20 minutes. Dichloromethane (116 mL) was added to the reaction mixture, and after sonication for 20 minutes, the solid was filtered and washed with dichloromethane. The obtained solid was dried under reduced pressure, and 2M hydrochloric acid (116 mL) and chloroform (116 mL) were added. Insoluble matter was filtered off and washed with acetone to obtain a brown solid of 2-(5-nitrocibenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 1.16 g, yield 56%). 1 H-NMR (400MHz, CDCl3) δ(ppm): 9.35(d,J=0.8Hz,1H),8.76(d,J=2.3Hz,1H),8.44(dd,J=9.2,2.3Hz,1H),7.96-7.89(m,2H),7.84-7.71(m,4H). (Reference example 6)

[0326] [ka]

[0327] Benzothiophene-2-carboxylic acid (5.17 g, 29.0 mmol) and N,N-dimethyl-4-aminopyridine (3.54 g, 29.0 mmol) were dissolved in N,N-dimethylformamide (175 mL) and stirred at room temperature for 5 minutes. To this solution, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (5.60 g, 29.0 mmol) was added and stirred at room temperature for 5 minutes, then 1,3-indanedione (1.41 g, 9.67 mmol) was added and stirred at room temperature for 120 hours. The reaction mixture was cooled to 0°C, and 2M hydrochloric acid (390 mL) cooled on ice was added. The precipitated solid was filtered and washed with 2M hydrochloric acid (300 mL) cooled on ice and water (300 mL). The obtained solid was dried under reduced pressure, dispersed in 200 mL of 1M aqueous sodium hydroxide solution, and irradiated with sonication for 20 minutes. Dichloromethane (200 mL) was added, and after sonication for 20 minutes, the solid was filtered and washed with dichloromethane. The obtained solid was dried under reduced pressure, dissolved in 2M hydrochloric acid (200 mL) and dichloromethane (200 mL), and after liquid-liquid separation, the aqueous layer was extracted with dichloromethane (200 mL). The organic and aqueous layers were combined and concentrated under reduced pressure, and the resulting crude was washed with hexane and then reprecipitated with acetone / hexane. The precipitated solid was reprecipitated with chloroform / hexane, the supernatant was separated and concentrated under reduced pressure to obtain a yellow solid of 2-(benzothiophen-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 1.00 g, yield 34%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.50(brs,1H),9.69(brs,1H),8.03(brd,J=7.9Hz,1H),7.92(brd,J=7.9Hz,1 H),7.93-7.85(m,2H),7.81-7.69(m,2H),7.52(ddd,J=7.9,7.1,1.2Hz,1H),7.45(ddd,J=7.9,7.1,1.1Hz,1H). (Reference example 7)

[0328] [ka]

[0329] Carbazole (4.18 g, 25.0 mmol), 4-fluorobenzonitrile (3.57 g, 29.5 mmol), and cesium fluoride (7.13 g, 46.9 mmol) were dissolved in dimethyl sulfoxide (35 mL) and stirred at 110 °C for 18 hours. The reaction mixture was poured into methanol (30 mL), to which methanol (120 mL) and water (100 mL) were added. The precipitated solid was filtered, washed with methanol and water, and dried under reduced pressure at 60 °C to obtain a white solid of 4-(9H-carbazole-9-yl)benzonitrile (yield 6.28 g, yield 94%). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.15(brd,J=7.7Hz,2H),7.91(brd,J=8.1Hz,2H) ,7.75(brd,J=8.1Hz,2H),7.48-7.41(m,2H),7.34(brd,J=8.1,8.1,2.0Hz,2H).

[0330] 4-(9H-carbazole-9-yl)benzonitrile (6.28 g, 23.4 mmol) and potassium hydroxide (18.9 g, 337 mmol) were dissolved in ethanol (85 mL) and water (35 mL), and the mixture was stirred at 100°C for 5 days. 2M hydrochloric acid (150 mL) was added to the reaction mixture, and the precipitated solid was filtered off and heated and dried to obtain a white solid of 4-(9H-carbazole-9-yl)benzoic acid (yield 6.84 g, yield quant.). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.35(brd,J=8.6Hz,2H),8.16(brd,J=7.6Hz,2H),7.75(brd,J=8.6Hz, 2H),7.51(brd,J=8.1Hz,2H),7.45(brdt,J=7.9,7.9,1.0Hz,2H),7.33(brd,J=7.2,7.2,1.1Hz,2H).

[0331] 4-(9H-carbazole-9-yl)benzoic acid (144 mg, 0.50 mmol) and N,N-diisopropylethylamine (263 μL, 1.5 mmol) were dissolved in N,N-dimethylformamide (9.0 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (228 mg, 6.00 mmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (219 mg, 1.50 mmol) was added and stirred at room temperature for 18 hours. The reaction mixture was cooled to 0°C, and 20 mL of ice-cold 2M hydrochloric acid was added. The precipitated solid was filtered off and washed with 20 mL of ice-cold 2M hydrochloric acid and 20 mL of water. The obtained solid was dried under reduced pressure, dispersed in 10 mL of 1 M sodium hydroxide aqueous solution, and sonicated for 10 minutes. Dichloromethane (10 mL) was added, and sonication was irradiated for 10 minutes. The solid was then filtered and washed with dichloromethane. The obtained solid was dried under reduced pressure, dissolved in 10 mL of 2 M hydrochloric acid and 10 mL of chloroform, and after liquid-liquid extraction, the aqueous layer was extracted with chloroform (10 mL x 3). The organic and aqueous layers were combined, dried over sodium sulfate, concentrated under reduced pressure, and recrystallized twice with chloroform / hexane to obtain a yellow solid of 2-[4-(9H-carbazole-9-yl)benzoyl]-1H-indene-1,3(2H)-dione (yield 109 mg, yield 53%). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.49(brd,J=8.7Hz,2H),8.16(brd,J=8.1Hz,2H),7.92(brdt,J=6.0,1.3Hz,2 H),7.83-7.74(m,4H),7.60(brd,J=8.2Hz,2H),7.46(brdt,J=7.0,1.1Hz,2H),7.34(brdt,J=7.8,0.9Hz,2H). (Reference example 8)

[0332] [ka]

[0333] 4-(diphenylamino)benzaldehyde (25.0 g, 91.5 mmol) was dissolved in acetone (640 mL) and water (160 mL) and heated to 60°C. Potassium permanganate (66.5 g, 421 mmol) was gradually added and the mixture was stirred at 60°C for 24 hours. The reaction mixture was concentrated under reduced pressure, water (500 mL) was added, and the mixture was filtered. 2M hydrochloric acid (150 mL) was added to the filtrate. The precipitated solid was filtered and dried by heating to obtain a white solid of 4-(diphenylamino)benzoic acid (yield 26.3 g, yield quant.). 1 H-NMR (400MHz, CDCl3) δ (ppm): 7.90 (brd, J=8.6Hz, 2H), 7.32 (brdd, J=7.2, 1.1Hz, 4H), 7.18-7.10 (m, 6H), 6.99 (brd, J=8.8Hz, 2H).

[0334] 4-(diphenylamino)benzoic acid (868 mg, 3.00 mmol) was dissolved in dichloromethane (15 mL). Oxalyl dichloride (386 μL, 4.50 mmol) and N,N-dimethylformamide (10 μL, 130 μmol) were added at 0°C, and the mixture was stirred for 4 hours while increasing the temperature to room temperature. The reaction mixture was concentrated under reduced pressure to obtain a white-orange solid of 4-(diphenylamino)benzoyl chloride. This crude product was used in the next reaction without further purification. 1 H-NMR (400MHz, CDCl3) δ (ppm): 7.90 (brd, J=9.3Hz, 2H), 7.36 (brdd, J=7.2, 0.9Hz, 4H), 7.23-7.16 (m, 6H), 6.93 (brd, J=9.1Hz, 2H).

[0335] Diisopropylamine (885 μL, 6.26 mmol) was dissolved in tetrahydrofuran (20 mL). After cooling this solution to 0°C, a hexane solution of n-butyllithium (2.80 M, 2.25 mL, 6.30 mmol) was added dropwise, and after cooling to -78°C, 1-(2-iodophenyl)ethanone (878 μL, 6.32 mmol) was added and the mixture was stirred for 1 hour. 4-(diphenylamino)benzoyl chloride was added to this solution and the mixture was stirred for 18 hours while increasing the temperature to room temperature. The reaction mixture was cooled to 0°C, 14.0 mL of 1 M hydrochloric acid was added, and after confirming that the reaction mixture was acidic, the aqueous layer was extracted three times with ethyl acetate. The organic layers were combined and dried over sodium sulfate, then concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a yellow solid of 1-[4-(diphenylamino)phenyl]-3-(2-iodophenyl)propane-1,3-dione (yield 791 mg, yield 51%). 1 H-NMR(400MHz,CDCl3)δ(ppm):16.42(brs,1H),7.95(dd,J=7.9Hz,0.9Hz,1H),7.80(brd,J=9.0Hz,2H),7.51(dd,J=7.6Hz,1 .8Hz,1H),7.42(dt,J=7.5Hz,1.1Hz,1H),7.33(brt,J=8.0Hz,4H),7.18-7.10(m,7H),7.02(brd,J=9.0Hz,2H),6.45(s,1H).

[0336] 1-(4-(diphenylamino)phenyl)-3-(2-iodophenyl)propane-1,3-dione (517 mg, 1.00 mmol), bis(acetonitrile)palladium(II) dichloride (7.78 mg, 30.0 μmol), 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (34.7 mg, 60.0 μmol), and tripotassium phosphate (425 mg, 2.00 mmol) were dissolved in dimethyl sulfoxide (2.5 mL), phenyl formate (218 μL, 1.96 mmol) was added, and the mixture was stirred at 95°C for 24 hours. The reaction mixture was cooled to room temperature, water (13 mL) was added, and the aqueous layer was extracted with ethyl acetate. 1 M hydrochloric acid was added to the organic layer, and after confirming that the reaction mixture was acidic, the aqueous layer was extracted three times with ethyl acetate. The organic and organic layers were dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a yellow solid of 2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dione (yield 167 mg, yield 40%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.24(brs,1H),8.20(d,J=9.0Hz,2H),7.84-7.79(m,2H) ,7.73-7.65(m,2H),7.35(brt,J=7.7Hz,4H),7.23-7.16(m,6H),7.52(brd,J=9.0Hz,2H). (Reference example 9)

[0337] [ka]

[0338] 2-hydroxy-1-naphthaldehyde (5.00 g, 29.0 mmol) and potassium carbonate (32.0 g, 116 mmol) were dissolved in N,N-dimethylformamide (76 mL), and ethyl bromoacetate (4.2 mL, 37.9 mmol) was added. The mixture was stirred at 140°C for 24 hours. After cooling to room temperature, 2M hydrochloric acid (150 mL) was added, and the precipitated solid was filtered off and washed with water (30 mL). The obtained solid was reprecipitated with acetone / hexane, and the precipitated solid was filtered off to obtain a brown solid of ethyl naphtho[2,1-b]furan-2-carboxylate (yield 2.85 g, yield 41%). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.17(d,J=8.1Hz,1H),8.03(s,1H),7.97(d,J=8.1Hz,1H) ,7.88(d,J=9.0Hz,1H),7.74-7.53(m,3H),4.49(q,J=7.3Hz,2H),7.59(t,J=7.3Hz,3H).

[0339] Ethyl naphtho[2,1-b]furan-2-carboxylate (810 mg, 3.37 mmol) was dissolved in tetrahydrofuran (5.0 mL), methanol (5.0 mL), and water (5.0 mL). Lithium hydroxide monohydrate (164 mg, 6.74 mmol) was added, and the mixture was stirred at room temperature for 22 hours. 2M hydrochloric acid (10 mL) was added to the reaction mixture, the precipitated solid was filtered, washed with water, and then recrystallized with chloroform. The precipitated solid was filtered and heated and dried to obtain a white solid of naphtho[2,1-b]furan-2-carboxylic acid (yield 558 mg, yield 78%). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.22-8.17(m,2H),7.98(t,J=8.0Hz,1H),7.92(d,J=9 .0Hz,1H),7.73(brd,J=9.2Hz,1H),7.68(brt,J=7.5Hz,1H),7.58(brt,J=7.6Hz,1H).

[0340] Naphtho[2,1-b]furan-2-carboxylic acid (628 mg, 2.96 mmol) and N,N-diisopropylethylamine (1.55 mL, 8.88 mmol) were dissolved in N,N-dimethylformamide (63 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (1.35 g, 3.55 mmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (1.29 g, 8.88 mmol) was added and stirred at room temperature for 3 days. The reaction mixture was cooled to 0°C, and 119 mL of ice-cold 2M hydrochloric acid was added. The precipitated solid was filtered off and washed with ice-cold 2M hydrochloric acid (90 mL) and water (90 mL). The obtained solid was washed with acetone and recrystallized with chloroform / hexane to obtain a yellow solid of 2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dione (yield 843 mg, yield 87%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.4(brs,1H),9.82(s,1H),8.38(d,J=8.8Hz,1H),7.98(t,J=8.8H z,2H),7.92(d,J=6.8Hz,1H),7.88(d,J=6.8Hz,1H),7.82-7.69(m,4H),7.59(brdt,J=7.3Hz,1H). (Reference example 10)

[0341] [ka]

[0342] Diphenylamine (502 mg, 2.97 mmol), ethyl 4-bromobenzoate (319 μL, 1.99 mmol), cesium carbonate (1.30 g, 3.99 mmol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (100 mg, 161 μmol), and palladium acetate (90 mg, 0.401 mmol) were dissolved in N,N-dimethylformamide (5.5 mL) and stirred at 80°C for 19 hours. The reaction mixture was diluted with ethyl acetate (50 mL), and the solid was removed by Celite filtration. The resulting filtrate was washed twice with 1 M hydrochloric acid (5 mL), twice with water (5 mL), and once with saturated saline solution (10 mL), and the resulting organic layer was concentrated under reduced pressure. The crude product obtained was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a yellow solid of ethyl 4-(diphenylamino)benzoate (yield 762 mg, yield 80%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.86(brd,J=8.9Hz,2H),7.30(brdd,J=8.4,1.1Hz,4H),7 .16-7.11(m,6H),6.99(brd,J=8.9Hz,2H),4.34(q,J=7.2Hz,2H),1.36(t,J=7.2Hz,3H).

[0343] Ethyl 4-(diphenylamino)benzoate (556 mg, 1.75 mmol) was dissolved in dichloromethane (6.0 mL), and aluminum chloride (1.05 g, 7.82 mmol) was added. Acetyl chloride (557 μL, 7.81 mmol) was then added dropwise at 0°C. The mixture was stirred for 18 hours while slowly raising the temperature from 0°C to room temperature. The reaction mixture was then poured into cold water (50 mL) and extracted three times with chloroform (20 mL). The resulting organic layers were combined and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a yellow solid of ethyl 4-[bis(4-acetylphenyl)amino]benzoate (yield 772 mg, yield quant.). 1H-NMR(400MHz,CDCl3)δ(ppm):7.98(brd,J=8.9Hz,2H),7.90(brd,J=8.8Hz,4H ),7.17-7.12(m,6H),4.38(q,J=7.2Hz,2H),2.58(s,6H),1.39(t,J=7.2Hz,3H).

[0344] Ethyl 4-[bis(4-acetylphenyl)amino]benzoate (772 mg, 1.92 mmol) was dissolved in tetrahydrofuran (3.0 mL), methanol (3.0 mL), and water (3.0 mL). Lithium hydroxide monohydrate (161 mg, 3.84 mmol) was added, and the mixture was stirred at room temperature for 16 hours. 2 M hydrochloric acid (2.0 mL) was added to the reaction mixture, and the precipitated solid was filtered off and washed with water. The mixture was then heated and dried under reduced pressure at 60°C to obtain a yellow solid of 4-[bis(4-acetylphenyl)amino]benzoic acid (yield 663 mg, yield 93%). 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.03 (brd, J=8.9Hz, 2H), 7.92 (brd, J=8.8Hz, 4H), 7.21-7.11 (m, 6H), 2.59 (s, 6H), 1.79 (brs, 1H).

[0345] 4-[bis(4-acetylphenyl)amino]benzoic acid (187 mg, 501 μmol) and N,N-diisopropylethylamine (263 μL, 1.55 mmol) were dissolved in N,N-dimethylformamide (9.0 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (228 mg, 600 μmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (219 mg, 1.50 mmol) was added and stirred at room temperature for 42 hours. 2M hydrochloric acid (5 mL) cooled on ice at 0°C was added to the reaction mixture, and the precipitated solid was filtered off and washed with 2M cold hydrochloric acid (5 mL) cooled on ice and water (5 mL). Acetone was added to the obtained solid, and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, methanol was added to the resulting crude material, insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The resulting solid was reprecipitated with methanol / water, and the precipitated solid was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a yellow solid of 2-{4-[bis(4-acetylphenyl)amino]benzoyl}-1H-indene-1,3(2H)-dione (yield 68.0 mg, yield 27%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.17(brs,1H)8.24(brd,J=8.9Hz,2H),7.93(brd,J =8.7Hz,4H),7.89-7.83(m,2H),7.78-7.69(m,2H),7.24-7.18(m,6H),2.60(s,6H). (Reference example 11)

[0346] [ka]

[0347] Palladium acetate (112 mg, 0.50 mmol) and tri-tert-butylphosphine (1.0 M, 1.50 mL, 1.50 mmol) were suspended in toluene (20 mL) and stirred at room temperature for 15 minutes. Methyl 4-aminobenzoate (1.51 g, 10.0 mmol), 4-iodobenzotrifluoride (4.40 mL, 30.0 mmol), and cesium carbonate (8.15 g, 25 mmol) were added, and the mixture was stirred at 120 °C for 24 hours. The reaction mixture was diluted with dichloromethane (70 mL), and the solid was removed by Celite filtration. Methanol (10 mL) and water (10 mL) were added to the obtained filtrate, and the precipitated solid was filtered off and washed with methanol to obtain a white solid of methyl 4-{bis[4-(trifluoromethyl)phenyl]amino}benzoate (yield 3.39 g, yield 77%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.96(d,J=8.9Hz,2H),7.55(brd,J=8.5Hz,4H),7.18(brd,J=8.3Hz,4H),6.11(brd,J=8.7Hz,2H),3.91(s,3H). 19 F-NMR (400MHz, CDCl3) δ (ppm): -62.1 (brs).

[0348] Methyl 4-{bis[4-(trifluoromethyl)phenyl]amino}benzoate (573 mg, 1.30 mmol) was dissolved in tetrahydrofuran (2.0 mL), methanol (2.0 mL), and water (2.0 mL). Lithium hydroxide monohydrate (109 mg, 2.60 mmol) was added, and the mixture was stirred at room temperature for 17 hours. 2 M hydrochloric acid (3.0 mL) was added to the reaction mixture, and the mixture was concentrated under reduced pressure and washed with water to obtain a white solid of 4-{bis[4-(trifluoromethyl)phenyl]amino}benzoic acid (yield 557 mg, yield quant.). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.01(brd,J=8.7Hz,2H),7.56(brd,J=8.5Hz,4H),7.21(brd,J=8.5Hz,4H),7.12(brd,J=8.3Hz,2H). 19 F-NMR (400MHz, CDCl3) δ (ppm): -62.2 (brs).

[0349] 4-{bis[4-(trifluoromethyl)phenyl]amino}benzoic acid (213 mg, 501 μmol) and N,N-diisopropylethylamine (263 μL, 1.55 mmol) were dissolved in N,N-dimethylformamide (9.0 mL) and stirred at room temperature for 5 minutes. To this solution, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (228 mg, 600 μmol) was added and stirred at room temperature for 5 minutes. Then, 1,3-indanedione (219 mg, 1.50 mmol) was added and stirred at room temperature for 11 hours. 2M hydrochloric acid (6 mL) cooled on ice at 0°C was added to the reaction mixture, and the precipitated solid was filtered off and washed with 2M cold hydrochloric acid (5 mL) and water (5 mL). Acetone was added to the obtained solid, and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, and the resulting crude product was washed with methanol. The obtained solid was recrystallized in acetone / hexane to obtain a yellow solid of 2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dione (yield 65.6 mg, yield 25%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.20(brs,1H),8.23(d,J=8.6Hz,2H),7.88-7.82(m,2H) ,7.77-7.69(m,2H),7.59(d,J=8.2Hz,4H),7.26(d,J=8.2Hz,4H),7.16(d,J=8.9Hz,2H). 19 F-NMR (400MHz, CDCl3) δ (ppm): -62.2 (brs). (Reference example 12)

[0350] [ka]

[0351] 4-Methoxybenzoic acid (1.52 g, 10.0 mmol) was dissolved in dichloromethane (50 mL). Oxalyl dichloride (1.29 mL, 15.0 mmol) and N,N-dimethylformamide (30 μL, 390 μmol) were added at 0°C, and the mixture was stirred for 4 hours while increasing the temperature to room temperature. The reaction mixture was concentrated under reduced pressure to obtain a colorless oily substance of 4-methoxybenzoyl chloride. This crude product was used in the next reaction without further purification. 1 H-NMR (400MHz, CDCl3) δ (ppm): 8.09 (d, J = 9.1 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 3.90 (s, 3H).

[0352] Diisopropylamine (2.95 mL, 21.0 mmol) was dissolved in tetrahydrofuran (60 mL). After cooling this solution to 0°C, a hexane solution of n-butyllithium (2.80 M, 7.50 mL, 21.0 mmol) was added dropwise, and the mixture was stirred for 20 minutes. After cooling the reaction mixture to -78°C, 1-(2-iodophenyl)ethanone (2.92 mL, 21.0 mmol) was added, and the mixture was stirred for 1 hour. To this solution, the previously obtained tetrahydrofuran (5.0 mL) solution of 4-methoxybenzoyl chloride was added, and the mixture was stirred for 20 hours while increasing the temperature to room temperature. After cooling the reaction mixture to 0°C, 2 M hydrochloric acid (20.0 mL) was added, and the aqueous layer was extracted three times with ethyl acetate (20 mL). The organic layers were combined, dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude product was washed with hexane and recrystallized with chloroform / hexane to obtain a yellow solid of 1-(2-iodophenyl)-3-(4-methoxyphenyl)propane-1,3-dione (yield 2.27 g, yield 60%). 1 H-NMR(400MHz,CDCl3)δ(ppm):16.36(brs,1H),7.98-7.92(m,3H),7.52(brdd,J=7.6Hz,1.6Hz,1H),7.43(dd d,J=7.5,7.5,1.0Hz,1H),7.13(ddd,J=7.7,7.7,1.8Hz,1H),7.33(d,J=9.0Hz,2H),6.49(s,1H),3.89(s,3H).

[0353] 1-(2-iodophenyl)-3-(4-methoxyphenyl)propane-1,3-dione (1.14 g, 3.00 mmol), bis(acetonitrile)palladium(II) dichloride (23.3 mg, 90.0 μmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (104 mg, 180 μmol), and tripotassium phosphate (1.27 g, 6.00 mmol) were suspended in dimethyl sulfoxide (7.5 mL), phenyl formate (654 μL, 6.00 mmol) was added, and the mixture was stirred at 95°C for 24 hours. The reaction mixture was cooled to room temperature, water (30 mL) and ethyl acetate (30 mL) were added, and the aqueous layer was separated. 2M hydrochloric acid (10 mL) was added to the aqueous layer, ethyl acetate (30 mL) was added, and after liquid-liquid extraction, the aqueous layer was extracted twice with ethyl acetate (30 mL). The organic layers were combined, dried over sodium sulfate, concentrated under reduced pressure, and the resulting crude product was recrystallized in acetone / hexane to obtain a yellow solid of 2-(4-methoxybenzoyl)-1H-indene-1,3(2H)-dione (yield 174 mg, yield 21%). 1 H-NMR (400MHz, CDCl3) δ (ppm): 15.26 (brs, 1H), 8.31 (d, J = 9.1 Hz, 2 H), 7.87-7.83 (m, 2 H), 7.76-7.67 (m, 2 H), 7.02 (d, J = 9.2 Hz, 2 H), 3.92 (s, 3 H). (Reference example 13)

[0354] [ka]

[0355] Diisopropylamine (3.40 mL, 20.0 mmol) was dissolved in tetrahydrofuran (57 mL). After cooling this solution to 0°C, a hexane solution of n-butyllithium (2.80 M, 7.10 mL, 20.0 mmol) was added dropwise, and the mixture was stirred for 30 minutes. After cooling the reaction mixture to -78°C, 1-(2-iodophenyl)ethanone (2.78 mL, 20.0 mmol) was added, and the mixture was stirred for 40 minutes. To this solution, a tetrahydrofuran (10.0 mL) solution of 2-naphthoyl chloride (1.91 g, 10.0 mmol) was added, and the mixture was stirred for 19.5 hours while increasing the temperature to room temperature. 1 M hydrochloric acid (45.0 mL) was added to the reaction mixture, and after liquid-liquid extraction, the aqueous layer was extracted twice with ethyl acetate (60 mL). The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a yellow solid of 1-(2-iodophenyl)-3-(2-naphthyl)propane-1,3-dione (yield 1.34 g, yield 34%). 1 H-NMR(400MHz,CDCl3)δ(ppm):16.26(brs,1H),8.53(brs,1H),8.01-7.87(m,5H),7.64-7.53(m,3 H),7.46(dd,J=7.5,7.5,1.1Hz,1H),7.13(ddd,J=7.6,7.6,1.6Hz,1H),6.72(s,1H),3.89(s,3H).

[0356] 1-(2-iodophenyl)-3-(2-naphthyl)propane-1,3-dione (1.34 g, 3.35 mmol), bis(acetonitrile)palladium(II) dichloride (26.1 mg, 101 μmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (116 mg, 200 μmol), and tripotassium phosphate (1.42 g, 6.70 mmol) were suspended in dimethyl sulfoxide (8.4 mL), phenyl formate (730 μL, 6.70 mmol) was added, and the mixture was stirred at 95°C for 24 hours. The reaction mixture was cooled to 0°C, and after liquid-liquid extraction with 1 M hydrochloric acid (10 mL), water (60 mL), and ethyl acetate (80 mL), the aqueous layer was extracted twice with ethyl acetate (80 mL). The organic and organic layers were washed with water (80 mL) and saturated brine (80 mL), and then dried over sodium sulfate. The mixture was concentrated under reduced pressure, and the resulting crude product was recrystallized in ethyl acetate / hexane to obtain a pale yellow solid of 2-(2-naphthoyl)-1H-indene-1,3(2H)-dione (yield 377 mg, yield 37%). 1 H-NMR(400MHz,CDCl3)δ(ppm):15.26(brs,1H),8.90(brs,1H),8.13(dd,J=8.7,1.8Hz,1H),8.04(brd,J=8.1Hz,1H),7.95( d,J=8.7Hz,1H),7.93-7.87(m,3H),7.79-7.71(m,2H),7.64(ddd,J=8.2,6.8,1.4Hz,1H),7.58(ddd,J=8.2,6.8,1.4Hz,1H). (Reference example 14)

[0357] [ka]

[0358] Tricyclohexylphosphine (1.66 g, 5.92 mmol) was dissolved in dichloromethane (10.0 mL), 30% hydrogen peroxide solution (3.00 mL) was added, and the mixture was stirred at room temperature for 1 hour. Water (15 mL) was added to the reaction mixture, and after separating the organic layer, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This procedure was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of tricyclohexylphosphine oxide (yield 1.24 g, yield 71%). 1 H-NMR(400MHz,CDCl3)δ(ppm):1.94-1.73(m,18H),1.48-1.25(m,15H). 31 P-NMR (162MHz, CDCl3)δ(ppm):50.0(s). (Reference example 15)

[0359] [ka]

[0360] Tri(o-tolyl)phosphine (1.01 g, 3.32 mmol) was dissolved in dichloromethane (10.0 mL), 30% hydrogen peroxide solution (1.00 mL) was added, and the mixture was stirred at room temperature for 2.5 hours. Water (10 mL) was added to the reaction mixture, and after separating the organic layer, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This procedure was repeated twice. The organic layers were combined, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of tri(o-tolyl)phosphine oxide (yield 448 mg, yield 42%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.43(brdd,J=7.5,7.4Hz,3H),7.32(brdd,J=7.5,4.1Hz,3H),7.19-7.05(m,6H),2.50(s,9H). 31 P-NMR (162MHz, CDCl3)δ(ppm):37.1(s). (Reference example 16)

[0361] [ka]

[0362] 412 mg, 1.00 mmol of 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl was dissolved in 5.00 mL of dichloromethane, and 2.40 mL of 30% hydrogen peroxide solution was added. The mixture was stirred at room temperature for 17 hours. 15 mL of water was added to the reaction mixture, and after separating the organic layer, 15 mL of chloroform was added to the aqueous layer, and the chloroform layer was separated. This procedure was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of dicyclohexyl(2',6'-dimethoxybiphenyl-2-yl)phosphine oxide (yield 386 mg, yield 90%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.54-7.46(m,1H),7.34-7.28(t,J=8.2Hz,1H),7.16-7.12(m,1H ),6.60(d,J=8.5Hz,6H),3.68(s,6H),1.79~1.39(m,12H),1.38-1.24(m,2H),1.20-1.01(m,6H). 31 P-NMR (162MHz, CDCl3)δ(ppm):46.6(s). (Reference example 17)

[0363] [ka]

[0364] (S)-[1,1'-binaphthalene]-2,2'-diirbis(diphenylphosphine) (2.00 g, 3.21 mmol) was dissolved in dichloromethane (100 mL), cooled to 0°C, and 30% hydrogen peroxide solution (6.60 mL) was added. The mixture was stirred at 0°C for 1 hour and then at room temperature for 24 hours. Water (75 mL) was added to the reaction mixture, and after separating the organic layer, the aqueous layer was extracted three times with chloroform (50 mL). The organic layers were combined, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was recrystallized in methanol / water to obtain a white solid of (S)-[1,1'-binaphthalene]-2,2'-diirbis(diphenylphosphine oxide) (yield 1.80 g, yield 86%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.85(dd,J=8.5,2.4Hz,2H),7.81(brd,J=8.1Hz,2 H),7.72-7.65(m,4H),7.46-7.31(m,12H),7.29-7.19(m,8H),6.82-6.77(m,4H). 31 P-NMR (162MHz, CDCl3)δ(ppm):28.5(s). (Reference example 18)

[0365] [ka]

[0366] 9,9-dimethyl-9H-xanthene-4,5-diirbis(diphenylphosphine) (1.16 g, 2.00 mmol) was dissolved in dichloromethane (10.0 mL), cooled to 0°C, and 30% hydrogen peroxide solution (1.24 mL) was added. The mixture was stirred for 3 hours while slowly increasing the temperature to room temperature. Water (10 mL) was added to the reaction mixture, and after separating the organic layer, the aqueous layer was extracted three times with chloroform (10 mL). The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was washed with hexane to obtain a white solid of 9,9-dimethyl-9H-xanthene-4,5-diirbis(diphenylphosphine oxide) (yield 1.20 g, yield 98%). 1H-NMR(400MHz,CDCl3)δ(ppm):7.59(brd,J=7.7Hz,2H),7.49-7.40(m,12H),7.36 -7.30(m,18H),6.97(ddd,J=7.7,7.7,2.0Hz,2H),6.89-6.78(m,2H),1.63(s,6H). 31 P-NMR (162MHz, CDCl3)δ(ppm):29.4(s). (Reference example 19)

[0367] [ka]

[0368] A 10 wt% hexane solution of tri(tert-butyl)phosphine (6.00 mL, 2.02 mmol) was added dropwise to a CH2Cl2 (12.0 mL) solution of 30% hydrogen peroxide (600 μL, 5.82 mmol) at 0°C, and the mixture was stirred at 0°C for 1 hour. Water (10 mL) and chloroform (12 mL) were added to the reaction mixture, and after liquid-liquid extraction, the mixture was extracted twice with chloroform (10 mL). The combined organic layers were washed with water (5 mL), dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain tri(tert-butyl)phosphine oxide (yield 467 mg, yield quant.) as a colorless oil. 1 H-NMR(400MHz,CDCl3)δ(ppm):1.38(d,J PH (=12.3Hz, 27H). 31 P-NMR (162MHz, CDCl3)δ(ppm):64.7(s). (Reference example 20)

[0369] [ka]

[0370] Tri(2,5-xylyl)phosphine (1.22 g, 3.5 mmol) was dissolved in anhydrous dichloromethane (10 mL), 30% hydrogen peroxide solution (3.0 mL) was added, and the mixture was stirred at room temperature for 1 hour. Water (15 mL) was added to the reaction mixture, and after liquid-liquid extraction, the mixture was extracted three times with chloroform (15 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of tri(2,5-xylyl)phosphine oxide (yield 1.14 g, yield 90%). 1 H-NMR(400MHz,CDCl3)δ(ppm):7.23-7.16(m,6H),7.01(d,J PH =14.2Hz,3H),2.38(s,9H),2.23(s,9H). 31 P-NMR (162MHz, CDCl3)δ(ppm):36.0(s). (Reference example 21)

[0371] [ka]

[0372] 716 mg, 1.5 mmol of 2-dicyclohexylphosphin-2',4',6'-triisopropylbiphenyl was dissolved in 5.0 mL of dichloromethane, and 3.6 mL of 30% hydrogen peroxide solution was added. The mixture was stirred at room temperature for 17 hours. 15 mL of water was added to the reaction mixture, and after separating the organic layer, 15 mL of chloroform was added to the aqueous layer, and the chloroform layer was separated. This procedure was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of dicyclohexyl(2',4',6'-triisopropylbiphenyl-2-yl)phosphine oxide (yield 588 mg, yield 80%). 1H-NMR(400MHz,CDCl3),δ(ppm):7.72-7.63(m,1H),7.48-7.36(m,2H),7.20-7.14(m,1H),7.01-6.95(m,2H),2.97-2.80(m,1H),2.45 -2.30(m,2H),1.93-1.79(m,4H),1.78-1.67(m,8H),1.44-1.33(m,4H),1.32-1.22(m,12H),1.21-1.08(m,6H),0.96(d,J=6.7Hz,6H). 31 P-NMR (162MHz, CDCl3), δ(ppm):44.4(s). (Reference example 22)

[0373] [ka]

[0374] 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (999 mg, 4.50 mmol) was mixed with ethanol (20 mL) and 1 M sodium hydroxide aqueous solution (4.5 mL, 4.5 mmol). Europium chloride hexahydrate (550 mg, 1.50 mmol) was added to this mixture and the mixture was stirred at room temperature for 30 minutes. Water (150 mL) was added to this reaction mixture and the mixture was stirred at 60°C for a further 30 minutes. The resulting solid was filtered and washed with water to obtain a white solid of diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (yield 695 mg, yield 54%). 19 F-NMR(376MHz,DMSO-d6)δ(ppm):-78.4(brs).ESI-MS(m / Z),MeOH:839.1[M+Na] + . (Reference example 23)

[0375] [ka]

[0376] 2,4,6-Trichlorotriazine (18.4 g, 100 mmol) and N,N-Diethylaniline (29.7 g, 199 mmol) were mixed and stirred at 70°C for 18 hours. After cooling to room temperature, warmed chloroform (200 mL) was added, the mixture was filtered, and the filtrate was allowed to stand. The precipitated solid was collected by filtration, washed with chloroform, and dried. The resulting crude product was recrystallized in acetone to obtain yellowish-brown crystals of 4-[4,6-Dichloro-1,3,5-Triadin-2-yl]-N,N-Diethylaniline (yield 1.54 g, yield 5.2%). 1 H-NMR(400MHz, CDCl3)δ(ppm): 8.31(brd,J=9.3Hz,2H),6.68(brd,J=9.3Hz,2H),3.47(q,J=7.1Hz,4H),1.24(t,J=7.1Hz,6H).

[0377] 4-[4,6-dichloro-1,3,5-triazin-2-yl]-N,N-diethylaniline (650 mg, 2.19 mmol) and 3,5-dimethylpyrazole (640 mg, 6.66 mmol) were dissolved in toluene (30 mL), and N,N-diisopropylethylamine (3.30 mL, 19.3 mmol) was added. The mixture was stirred at 80°C for 12 hours. After cooling to room temperature, the solid was filtered, washed with chilled acetonitrile, and dried to obtain a pale yellow powder of 4-[4,6-bis(3,5-dimethyl-1H-pyrazole-1-yl)-1,3,5-triazin-2-yl]-N,N-diethylaniline (yield 638 mg, yield 70%). 1 H-NMR(400MHz,CDCl3)δ(ppm):8.40(brd,J=9.1Hz,2H),6.72(brd,J=9.3Hz,2H),6.0 8(brs,2H),3.47(q,J=7.1Hz,4H),2.85(brs,6H),2.35(s,6H),1.24(t,J=7.1Hz,6H). (Synthesis Example 1)

[0378] [ka]

[0379] Europium acetate n-hydrate (187 mg, 500 μmol as 2.5-hydrate) and triphenylphosphine oxide (278 mg, 1.00 mmol) were mixed with methanol (10 mL) and stirred at room temperature for 1 hour. 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (435 mg, 1.50 mmol) obtained in Reference Example 1 was added to the reaction mixture. 14.8 M aqueous ammonia (100 μL, 1.48 mmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water and methanol. The obtained solid was reprecipitated with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-1) (yield 371 mg, yield 48%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -78.2 (brs). ESIMS (m / Z), MeOH: 1287.3 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 2)

[0380] [ka]

[0381] Europium acetate n-hydrate (187 mg, 500 μmol as 2.5-hydrate) and triphenylphosphine oxide (278 mg, 1.00 mmol) were mixed with methanol (10 mL) and stirred at room temperature for 1 hour. 2-(7-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (480 mg, 1.50 mmol) obtained in Reference Example 2 was added to the reaction mixture. 14.8 M aqueous ammonia (100 μL, 1.48 mmol) was added dropwise and stirred at room temperature for 18 hours. The reaction mixture was concentrated under reduced pressure and washed with water. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(7-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-2) (yield 210 mg, yield 25%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -58.6 (brs). ESIMS (m / Z), MeOH: 1347.9 {M-[2-(7-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 3)

[0382] [ka]

[0383] Europium acetate n-hydrate (112 mg, 300 μmol as 2.5-hydrate) and 2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (288 mg, 900 μmol) obtained in Reference Example 3 were suspended in ethanol (11.4 mL) and water (3.6 mL). Then, 1 M sodium hydroxide aqueous solution (900 μL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-3) (yield 252 mg, yield 73%). The obtained crude product was used directly in the next reaction without further purification. ESIMS(m / Z),MeOH:1131.0[M-2H2O+Na] + .

[0384] Diaquatris[2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-3 (252 mg, 220 μmol) and triphenylphosphine oxide (122 mg, 440 μmol) were dissolved in acetone (22 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, reprecipitated with acetone / hexane, and washed with methanol to obtain a yellow solid of tris[2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-3) (yield 60.0 mg, yield 16%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -128.2 (brs). ESIMS (m / Z), MeOH: 1347.1 {M-[2-(6-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 4)

[0385] [ka]

[0386] Europium acetate n-hydrate (75.0 mg, 200 μmol as 2.5-hydrate) and 2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (192 mg, 600 μmol) obtained in Reference Example 4 were suspended in ethanol (7.6 mL) and water (2.5 mL). Then, 1 M sodium hydroxide aqueous solution (600 μL) was added, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and after centrifugation, the supernatant was removed and heated and dried to obtain the yellow solid diaquatris[2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-4). The obtained crude product was used directly in the next reaction without further purification. ESIMS(m / Z),MeOH:1131.0[Eu(3-hydroxy-2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1-onato)3+Na] + .

[0387] The obtained diaquatris[2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-4) and triphenylphosphine oxide (111 mg, 402 μmol) were dissolved in acetone (20 mL) and stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and reprecipitation was repeated three times with acetone / hexane to obtain a yellow solid of tris[2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-4) (yield 40.8 mg, yield 12%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -75.5 (brs). ESIMS (m / Z), MeOH: 1348.1 {M-[2-(5-methoxybenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 5)

[0388] [ka]

[0389] Europium acetate n-hydrate (187 mg, 500 μmol as 2.5-hydrate) and triphenylphosphine oxide (278 mg, 1.00 mmol) were mixed with dichloromethane (30 mL) and stirred at room temperature for 1 hour. 2-(5-nitrobenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (501 mg, 1.49 mmol) obtained in Reference Example 5 was added to the reaction mixture. 14.8 M aqueous ammonia (100 μL, 1.48 mmol) was added dropwise and stirred at room temperature for 18 hours. The reaction mixture was concentrated under reduced pressure and washed with water. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of [2-(5-nitrobenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-5) (yield 513 mg, yield 60%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -80.3 (brs). ESIMS (m / Z), MeOH: 1377.8 {M-[2-(5-nitrobenzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 6)

[0390] [ka]

[0391] Europium acetate n-hydrate (187 mg, 500 μmol as 2.5-hydrate) and triphenylphosphine oxide (278 mg, 1.01 mmol) were mixed with methanol (10 mL) and stirred at room temperature for 1 hour. 2-(benzothiophene-2-carbonyl)-1H-indene-1,3(2H)-dione (421 mg, 1.37 mmol) obtained in Reference Example 6 was added to the reaction mixture. 14.8 M aqueous ammonia (100 μL, 1.48 mmol) was added dropwise, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was concentrated under reduced pressure, washed with water, and then washed with methanol. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzothiophen-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-6) (yield 602 mg, yield 74%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -72.2 (brs). ESIMS (m / Z), MeOH: 1390.1 {M-[2-(benzothiophen-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 7)

[0392] [ka]

[0393] Europium acetate n-hydrate (37.0 mg, 989 μmol as 2.5-hydrate) and triphenylphosphine oxide (55.0 mg, 199 μmol) were mixed with methanol (2.0 mL) and stirred at room temperature for 1 hour. 2-[4-(9H-carbazole-9-yl)benzoyl]-1H-indene-1,3(2H)-dione (123 mg, 296 μmol) obtained in Reference Example 7 was added to the reaction mixture. 14.8 M aqueous ammonia (250 μL, 370 μmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of tris{2-[4-(9H-carbazole-9-yl)benzoyl]-1H-indene-1,3(2H)-dionato}bis(triphenylphosphine oxide)europium(III)(1a-7) (yield 132 mg, yield 69%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -76.9 (brs). ESIMS (m / Z), MeCN: 1537.9 (M-{2-[4-(9H-carbazole-9-yl)benzoyl]-1H-indene-1,3(2H)-dionato}) + . (Synthesis Example 8)

[0394] [ka]

[0395] Europium acetate n-hydrate (37.4 mg, 100 μmol as 2.5-hydrate) and 2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dione (125 mg, 299 μmol) obtained in Reference Example 8 were suspended in ethanol (9.0 mL) and water (3.0 mL). Then, 1 M sodium hydroxide aqueous solution (300 μL) was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris{2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dionato}europium(III)(1aq-8). The obtained crude product was used directly in the next reaction without further purification. The obtained diaquatris{2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dionato}europium(III)(1aq-8) and triphenylphosphine oxide (55.7 mg, 202 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation was performed with acetone / hexane. The precipitated solid was removed by filtration, hexane was added to the filtrate, and the precipitated solid was filtered off. The obtained solid was reprecipitation with chloroform / hexane, and the supernatant was removed to obtain the orange solid tris{2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dionato}bis(triphenylphosphine oxide)europium(III)(1a-8) (yield 48.0 mg, yield 25%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -72.4 (brs). ESIMS (m / Z), MeOH: 1540.5 (M-{2-[4-(diphenylamino)benzoyl]-1H-indene-1,3(2H)-dionato}) + . (Synthesis Example 9)

[0396] [ka]

[0397] Europium acetate n hydrate (122 mg, 337 μmol as 2.5 hydrate) and 2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dione (294 mg, 864 μmol) obtained in Reference Example 9 were suspended in ethanol (11.4 mL) and water (3.6 mL). Then, 1 M sodium hydroxide aqueous solution (900 μL) was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain a yellowish-green solid of diaquatris[2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-9) (206 mg, yield 57%). The resulting crude product was used directly in the next reaction without further purification.

[0398] The obtained diaquatris[2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-9) and triphenylphosphine oxide (94.6 mg, 343 μmol) were dissolved in acetone (17 mL) and stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, reprecipitation was performed with acetone / hexane, and the precipitated solid was filtered off. The obtained solid was heated and dried to obtain a yellow solid of tris[2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)europium(III)(1a-9) (yield 164 mg, yield 56%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -75.6 (brs). ESIMS (m / Z), MeOH: 1387.2 {M-[2-(naphtho[2,1-b]furan-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 10)

[0399] [ka]

[0400] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and tricyclohexylphosphine oxide (593 mg, 2.00 mmol) obtained in Reference Example 14 were mixed with methanol (20 mL) and stirred at room temperature for 1 hour. 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 was added to the reaction mixture. 14.8 M aqueous ammonia (330 μL, 4.88 mmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, washed with water, and then washed with methanol. The obtained solid was dissolved in chloroform and filtered to remove insoluble matter. The chloroform filtrate was then concentrated under reduced pressure to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(tricyclohexylphosphine oxide)europium(III)(1a-10) (yield 965 mg, yield 60%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -67.0 (brs). ESIMS (m / Z), MeOH: 1322.0 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 11)

[0401] [ka]

[0402] Europium acetate n-hydrate (112 mg, 299 μmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (261 mg, 900 μmol) obtained in Reference Example 1 were suspended in ethanol (11.4 mL) and water (3.6 mL). Then, 1 M sodium hydroxide aqueous solution (900 μL) was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered, and the filtered solid was washed with water, and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 353 mg, yield quant.). The obtained crude product was used directly in the next reaction without further purification.

[0403] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (353 mg, 335 μmol) and 1,8-bis(diphenylphosphinyl)naphthalene (159 mg, 301 μmol) were dissolved in acetone (30 mL) and stirred at room temperature for 19 hours. Hexane was added to the reaction mixture, the precipitate was filtered off and heated and dried to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](1,8-bis(diphenylphosphinyl)naphthalene)europium(III)(1a-11) (yield 403 mg, yield 87%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -31.4 (brs). ESIMS (m / Z), MeOH: 1259.8 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + Furthermore, single-crystal X-ray structural analysis was performed on tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](1,8-bis(diphenylphosphinyl)naphthalene)europium(III). The results of the single-crystal X-ray structural analysis are shown below, and the resulting crystal structure is shown in Figure 19.

[0404] Orthorhombic (PbCA) a = 13.5040(3) Å b = 50.3912 (12) Å c = 17.6593 (4) Å V = 15576.3 (6) Å 3 Z=8 R1 = 0.1259 wR2 = 0.3058 (Synthesis Example 12)

[0405] [ka]

[0406] Europium acetate n-hydrate (112 mg, 299 μmol as 2.5-hydrate) and 1,10-phenanthroline (54.1 mg, 301 μmol) were mixed with methanol (6.0 mL) and stirred at room temperature for 1 hour. 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (261 mg, 0.900 mmol) obtained in Reference Example 1 was added to the reaction mixture. 14.8 M aqueous ammonia (75.0 μL, 1.11 mmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](1,10-phenanthroline)europium(III)(1a-12) (yield 328 mg, yield 91%). 1 ¹H-NMR (400MHz, CD2Cl2) δ (ppm): 9.91 (brs, 2H), 9.10 (brs, 2H), 8.17-8.08 (m, 5H), 7.87 (brd, J=7.0Hz, 2H), 7.64 (brt, J=7.4Hz, 3H), 7.53 (brd, J=7.9Hz, 3H), 7.20 (brt, J=7.4Hz, 3H), 7.00 (brt, J=7.4Hz, 3H), 6.94-6.86 (m, 6H), 6.13 (brd, J=6.6Hz, 3H), 5.47 (brs, 3H). ESIMS (m / Z), MeOH: 910 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionate]} +,1223.7[M+Na] + . (Synthesis Example 13)

[0407] [ka]

[0408] Europium acetate n hydrate (100 mg, 267 μmol as 2.5 hydrate) and dipyride[3,2-a:2',3'-c]phenazine (75.4 mg, 267 μmol) were added to methanol (5.0 mL) and the mixture was stirred at room temperature for 1 hour. 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (230 mg, 792 μmol) obtained in Reference Example 1 was added to the reaction mixture. 14.8 M aqueous ammonia (80 μL, 1.18 mmol) was added dropwise and the mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water and methanol. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](dipyrido[3,2-a:2',3'-c]phenazine)europium(III)(1a-13) (yield 144 mg, yield 41%). 1 H-NMR(400MHz,CD2Cl2)δ(ppm):11.12(brs,2H),10.17(brs,2H),8.99(brs,2H),8.74-8.66(m, 3H),8.38(brs,2H),8.24(brs,2H),7.84-7.76(m,3H),7.55(brd,J=8.9Hz,3H),7.15-7.08(m,3 H), 7.00-6.93 (m, 3H), 6.91-6.84 (m, 3H), 6.80 (brd, J=7.0Hz, 3H), 6.20 (brd, J=7.0Hz, 3H), 5.40-5.31 (m, 3H). ESIMS (m / Z), MeOH: 1013.5 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 14)

[0409] [ka]

[0410] Europium acetate n-hydrate (112 mg, 299 μmol as 2.5-hydrate) and 2,2'-bipyridyl (46.9 mg, 300 μmol) were mixed with methanol (6.0 mL) and stirred at room temperature for 1 hour. 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (261 mg, 878 μmol) obtained in Reference Example 1 was added to the reaction mixture. 14.8 M aqueous ammonia (75 μL, 1.11 mmol) was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water and acetone. The obtained solid was reprecipitation with acetone / hexane to obtain a yellow solid of (2,2'-bipyridyl)tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-14) (yield 155 mg, yield 44%). ESIMS(m / Z),MeOH:887.3{M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + ,1200.5[M+Na] + . (Synthesis Example 15)

[0411] [ka]

[0412] Europium acetate n-hydrate (74 mg, 198 μmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (174 mg, 598 μmol) obtained in Reference Example 1 were suspended in ethanol (5.0 mL) and water (1.5 mL). Then, 1 M sodium hydroxide aqueous solution (600 μL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-1) (yield 151 mg, yield 71%). The obtained crude product was used directly in the next reaction without further purification.

[0413] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-1) (106 mg, 101 μmol) and bis[2-[(oxo)diphenylphosphino]phenyl] ether (57 mg, 99.9 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato](bis{2-[(oxo)diphenylphosphino]phenyl} ether)europium(III)(1a-34) (yield 144 mg, yield 90%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -91.3 (brs). ESIMS (m / Z), MeOH: 1301.2 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 16)

[0414] [ka]

[0415] Under ice cooling, trifluoroacetic anhydride (5.07 mL, 36.0 mmol) was added to a chloroform (28 mL) solution of imidazole (6.13 g, 90.0 mmol), and then a chloroform solution of 1,3-indanedione (1.50 M, 20.0 mL) was added dropwise over 2 hours. After stirring for 1 hour while slowly raising the temperature to room temperature, the precipitated solid was collected by suction filtration, washed with chloroform, and dried under reduced pressure to obtain a pale yellow solid of imidazolium [2-(trifluoroacetyl)-1H-indene-1,3(2H)-dionato] (containing 1.3 molar equivalents of imidazolium trifluoroacetate) (yield 14.3 g, yield 87%). The obtained crude product was used directly in the next reaction without further purification. 1 H-NMR(400MHz,Acetone-d6)δ(ppm):9.56(brs,5H),9.00(brs,2H),7.71(brd,4.6H),7.61-7.59(m,4H). 19 F-NMR (376MHz, Acetone-d6) δ (ppm): -74.2 (s, 3F), -75.8 (s, 3.9F).

[0416] Europium acetate n-hydrate (1.12 g, 3.00 mmol as 2.5-hydrate) and triphenylphosphine oxide (1.67 g, 6.00 mmol) were mixed with methanol (15 mL) and stirred at room temperature for 1 hour. Imidazolium [2-(trifluoroacetyl)-1H-indene-1,3(2H)-dionato] (containing 1.3 molar equivalents of imidazolium trifluoroacetate, 4.92 g, 9.00 mmol) was added to the reaction mixture and stirred at room temperature for 3 hours. The reaction solution was poured into water, and the precipitated solid was removed by suction filtration and washed with water. This solid was suspended in methylcyclohexane, azeotropic dehydration was performed, and after cooling, the solid was collected by suction filtration to obtain a pale purple solid of bis(triphenylphosphine oxide)tris[2-(trifluoroacetyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-35) (yield 3.68g, yield 86%). 19 F-NMR(376MHz,CDCl3)δ(ppm):-76.0(brs). 31P-NMR(162MHz,CDCl3)δ(ppm):-90.4(brs).ESIMS(m / Z),MeOH:1455.1[M+Na] + ,1191.2{M-[2-(trifluoroacetyl)-1H-indene-1,3(2H)-dionato} + . (Synthesis Example 17)

[0417] [ka]

[0418] Europium acetate n-hydrate (74 mg, 198 μmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (174 mg, 599 μmol) obtained in Reference Example 1 were suspended in ethanol (5.0 mL) and water (1.5 mL). Then, 1 M sodium hydroxide aqueous solution (600 μL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water, and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III) (1aq-1) (yield 151 mg, yield 71%). The obtained crude product was used directly in the next reaction without further purification.

[0419] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (211 mg, 198 μmol) and triphenylphosphine oxide (111 mg, 402 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato][bis(triphenylphosphine oxide)]europium(III)(1a-1) (yield 120 mg, yield 38%). 31P-NMR (162 MHz, CDCl3) δ (ppm): -78.2 (brs). ESIMS (m / Z), MeOH: 1287.3 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 18)

[0420] [ka]

[0421] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0422] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (211 mg, 200 μmol) and tri(o-tolyl)phosphine oxide obtained in Reference Example 15 (128 mg, 400 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis[tri(o-tolyl)phosphine oxide]europium(III)(1a-37) (yield 282 mg, yield 85%). 31P-NMR (162 MHz, CDCl3) δ (ppm): -95.9 (brs). ESIMS (m / Z), MeCN: 1372.7 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 19)

[0423] [ka]

[0424] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0425] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (106 mg, 101 μmol) and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine oxide (85.0 mg, 199 μmol) obtained in Reference Example 16 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine oxide) europium(III)(1a-44) (yield 119 mg, yield 64%).31 P-NMR (162 MHz, CDCl3) δ (ppm): -74.4 (brs). ESIMS (m / Z), MeCN: 1584.0 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 20)

[0426] [ka]

[0427] Europium acetate n-hydrate (16.8 mg, 44.9 μmol as 2.5-hydrate) and 2-{4-[bis(4-acetylphenyl)amino]benzoyl}-1H-indene-1,3(2H)-dione (68.0 mg, 136 μmol) obtained in Reference Example 10 were suspended in ethanol (10 mL) and water (3 mL). Then, 135 μL of 1 M sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris{2-[4-(bis(4-acetylphenyl)amino)benzoyl]-1H-indene-1,3(2H)-dionato}europium(III)(1aq-16) (yield 52.0 mg, yield 68%). The obtained crude product was used directly in the next reaction without further purification.

[0428] Diaquatris(2-{4-[bis(4-acetylphenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato) europium(III)(1aq-16) (52.0 mg, 28.0 μmol) and triphenylphosphine oxide (17.0 mg, 61.6 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane. The obtained solid was dissolved in ethanol, insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of tris(2-{4-[bis(4-acetylphenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato)[bis(triphenylphosphine oxide)] europium(III)(1a-22) (yield 46.0 mg, yield 46%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -73.0 (brs). ESIMS (m / Z), MeOH: 1711.2 [M-(2-{4-[bis(4-acetylphenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato)] + . (Synthesis Example 21)

[0429] [ka]

[0430] Europium acetate n-hydrate (32.2 mg, 86.0 μmol as 2.5-hydrate) and 2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dione (138 mg, 259 μmol) obtained in Reference Example 11 were suspended in ethanol (15 mL) and water (5 mL). Then, 1 M sodium hydroxide (259 μL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris{2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato}europium(III)(1aq-22) (yield 88.0 mg, yield 55%). The resulting crude product was used directly in the next reaction without further purification.

[0431] Diaquatris{2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato}europium(III)(1aq-22) (88.0 mg, 48.0 μmol) and triphenylphosphine oxide (26.7 mg, 95.9 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitated twice with chloroform / hexane to obtain a yellow solid of tris(2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato)[bis(triphenylphosphine oxide)]europium(III)(1a-28) (yield 55.0 mg, yield 48%). 31 P-NMR (162MHz, CDCl3) δ (ppm): -75.2 (brs). 19 F-NMR (400MHz, CDCl3) δ (ppm): -62.0 (brs). ESIMS (m / Z), MeOH: 1812.9 [M-(2-{4-[bis(4-(trifluoromethyl)phenyl)amino]benzoyl}-1H-indene-1,3(2H)-dionato)] + . (Synthesis Example 22)

[0432] [ka]

[0433] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0434] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1)(106 mg, 101 μmol) and (S)-[1,1'-binaphthalene]-2,2'-diirbis(diphenylphosphine oxide)(65.0 mg, 100 μmol) obtained in Reference Example 17 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of {(S)-[1,1'-binaphthalene]-2,2'-diirbis(diphenylphosphine oxide)}tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-45) (yield 98.6 mg, yield 59%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -58.8 (brs). ESIMS (m / Z), MeOH: 1385.4 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 23)

[0435] [ka]

[0436] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0437] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (106 mg, 101 μmol) and 9,9-dimethyl-9H-xanthene-4,5-diirbis(diphenylphosphine oxide) (61.0 mg, 100 μmol) obtained in Reference Example 18 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of [9,9-dimethyl-9H-xanthene-4,5-diirbis(diphenylphosphine oxide)]tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-82) (yield 128 mg, yield 78%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -84.5 (brs). ESIMS (m / Z), MeOH: 1341.5 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 24)

[0438] [ka]

[0439] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0440] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (106 mg, 101 μmol) and tri-tert-butylphosphine oxide (43.7 mg, 200 μmol) obtained in Reference Example 19 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of bis(tri-tert-butylphosphine oxide)tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-79) (yield 87.3 mg, yield 60%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -45.5 (brs). ESIMS (m / Z), MeOH: 1167.6 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 25)

[0441] [ka]

[0442] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0443] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (106 mg, 101 μmol) and tri(2,5-xylyl)phosphine oxide (72.4 mg, 200 μmol) obtained in Reference Example 20 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis[tri(2,5-xylyl)phosphine oxide]europium(III)(1a-40) (yield 163 mg, yield 93%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -98.9 (brs). ESIMS (m / Z), MeCN: 1455.3 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 26)

[0444] [ka]

[0445] Europium acetate n-hydrate (374 mg, 1.00 mmol as 2.5-hydrate) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (871 mg, 3.00 mmol) obtained in Reference Example 1 were suspended in ethanol (38 mL) and water (13 mL). Then, 1 M sodium hydroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (yield 1.00 g, yield 97%). The obtained crude product was used directly in the next reaction without further purification.

[0446] Diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-1) (106 mg, 101 μmol) and dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine oxide (72.4 mg, 200 μmol) obtained in Reference Example 21 were dissolved in acetone (10 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain a yellow solid of bis[dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine oxide]tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]europium(III)(1a-47) (yield 163 mg, yield 93%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -98.9 (brs). ESIMS (m / Z), MeCN: 1455.3 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 27)

[0447] [ka]

[0448] Europium acetate n-hydrate (77.4 mg, 206 μmol as 2.5-hydrate) and 2-(4-methoxybenzoyl)-1H-indene-1,3(2H)-dione (174 mg, 620 μmol) obtained in Reference Example 12 were suspended in ethanol (7.6 mL) and water (2.6 mL). Then, 1 M sodium hydroxide aqueous solution (620 μL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered, and the filtered solid was washed with water, and then with ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(4-methoxybenzoyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-30) (yield 198 mg, yield 94%). The obtained crude product was used directly in the next reaction without further purification.

[0449] Diaquatris[2-(4-methoxybenzoyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-30) (198 mg, 193 μmol) and triphenylphosphine oxide (108 mg, 387 μmol) were dissolved in acetone (21 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with acetone / hexane to obtain a yellow solid of tris[2-(4-methoxybenzoyl)-1H-indene-1,3(2H)-dionato][bis(triphenylphosphine oxide)]europium(III)(1a-103) (yield 150 mg, yield 16%). 31 P-NMR (162 MHz, CDCl3) δ (ppm): -72.4 (brs). ESIMS (m / Z), MeOH: 1267.5 {M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 28)

[0450] [ka]

[0451] Europium acetate n-hydrate (157 mg, 419 μmol as 2.5-hydrate) and 2-(2-naphthoyl)-1H-indene-1,3(2H)-dione (377 mg, 1.26 mmol) obtained in Reference Example 13 were suspended in ethanol (15.7 mL) and water (5.2 mL). Then, 1.26 mL of 1 M aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 18 hours. After distilling off the ethanol, water was added to the reaction mixture and filtered. The filtered solid was washed with water, and then with a very small amount of ethanol. The washed solid was heated and dried to obtain the yellow solid diaquatris[2-(2-naphthoyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-43) (yield 412 mg, yield 91%). The obtained crude product was used directly in the next reaction without further purification.

[0452] Diaquatris[2-(2-naphthoyl)-1H-indene-1,3(2H)-dionato]europium(III)(1aq-43) (397 mg, 365 μmol) and triphenylphosphine oxide (203 mg, 731 μmol) were dissolved in acetone (7.3 mL) and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and reprecipitation with chloroform / hexane to obtain the brown amorphous tris[2-(2-naphthoyl)-1H-indene-1,3(2H)-dionato][bis(triphenylphosphine oxide)]europium(III)(1a-106) (yield 531 mg, yield 90%). 31 P-NMR(162MHz,CDCl3)δ(ppm):-75.2(brs).ESIMS(m / Z),MeCN:1627.8[M+Na] + . (Synthesis Example 29)

[0453] [ka]

[0454] 81.6 mg, 200 μmol of terbium acetate tetrahydrate and 111 mg, 400 μmol of triphenylphosphine oxide were mixed with 10 mL of methanol and stirred at room temperature for 1 hour. 174 mg, 600 μmol of 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione obtained in Reference Example 1 was added to the reaction mixture. 40.5 μL, 600 μmol of 14.8 M aqueous ammonia was added dropwise and stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure and washed with water and methanol. The resulting solid was reprecipitated with chloroform / hexane to obtain the yellow solid tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]bis(triphenylphosphine oxide)terbium(III)(1a-31) (yield 296 mg, yield 93%). ESIMS(m / Z),MeOH:1293.6{M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Example 30)

[0455] [ka]

[0456] Gadolinium chloride hexahydrate (42.2 mg, 114 μmol) and 2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dione (98.8 mg, 340 μmol) obtained in Reference Example 1 were suspended in ethanol (20 mL), and then 1 M sodium hydroxide aqueous solution (320 μL) was added. The mixture was stirred at room temperature for 4 hours. The solid precipitated in the reaction mixture was filtered by suction, washed with water, and heated and dried to obtain the yellow solid diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]gadolinium(III)(1aq-25) (yield 37.6 mg, yield 31%). The obtained crude product was used directly in the next reaction without further purification.

[0457] The obtained diaquatris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]gadolinium(III)(1aq-25) (37.6 mg, 35.0 μmol) and triphenylphosphine oxide (19.7 mg, 71.4 μmol) were dissolved in acetone (10 mL) and stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and reprecipitation was repeated three times with acetone / hexane to obtain a yellow solid of tris[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato][bis(triphenylphosphine oxide)]gadolinium(III)(1a-32) (yield 22.9 mg, yield 41%). ESIMS(m / Z),MeOH:1326.1[M-(triphenylphosphine oxide)+Na] + ,1292.3{M-[2-(benzofuran-2-carbonyl)-1H-indene-1,3(2H)-dionato]} + . (Synthesis Comparison Example 1)

[0458] [ka]

[0459] The compound was synthesized according to Non-Patent Literature 3. Diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (667 mg, 800 μmol) obtained in Reference Example 22 and 4-[4,6-bis(3,5-dimethyl-1H-pyrazole-1-yl)-1,3,5-triazine-2-yl]-N,N-diethylaniline (334 mg, 800 μmol) obtained in Reference Example 23 were combined with tetrahydrofuran (160 mL) and stirred at room temperature for 2 hours. The reaction mixture was filtered, the residue was washed with tetrahydrofuran, and the mixture was dried under reduced pressure at room temperature. The crude product obtained was recrystallized twice (hexane / ethyl acetate and hexane / chloroform) to obtain the yellow powder bis{4-[4,6-bis(3,5-dimethyl-1H-pyrazole-1-yl)-1,3,5-triazine-2-yl]-N,N-diethylaniline}tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (yield 808 mg, yield 82%). 19 F-NMR (376MHz, CDCl3) δ (ppm): -81.1 (brs). ESIMS (m / Z): 1008.9 [M-(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)] + .

[0460] Evaluation Examples Samples for UV-Vis emission spectrum measurement of the rare earth complexes of the present invention were prepared by dissolving the rare earth complexes obtained in the synthesis examples and comparative examples in spectroscopic chloroform or toluene at a predetermined concentration and packing the solution into a 1 cm quartz cell for spectroscopic analysis.

[0461] Figures 1-18 show the measurement results of the UV-Vis· emission spectra of the rare earth complexes obtained in the synthesis examples and comparative examples. The emission spectrum measurement conditions were: excitation light of 350 nm or 420 nm, excitation-side slit of 1 nm, and fluorescence-side slit of 3 nm.

[0462] The acid resistance test of the rare earth complex of the present invention was evaluated by calculating the ratio of emission intensity at the maximum emission wavelength before and after the addition of benzoic acid. First, 3 mL of a 0.01 mM methanol solution of the rare earth complex was packed into a 1 cm quartz cell for spectroscopic analysis, and the emission spectrum of the rare earth complex before the addition of benzoic acid was measured with excitation light at 380 nm, excitation slit at 5 nm, and fluorescence slit at 5 nm. Then, 5 μL of a 0.01 M methanol solution of benzoic acid was added to the 1 cm quartz cell for spectroscopic analysis containing the 0.01 mM methanol solution of the rare earth complex, and after standing for 2 hours, the emission spectrum of the rare earth complex after the addition of benzoic acid was measured with excitation light at 380 nm, excitation slit at 5 nm, and fluorescence slit at 5 nm. The ratio of emission intensity was calculated from the emission intensity at the maximum emission wavelength before and after the addition of benzoic acid, and the results are summarized in Table 1. Emission intensity ratio (%) = (Emission intensity at maximum emission wavelength after benzoic acid addition) / (Emission intensity at maximum emission wavelength before benzoic acid addition) × 100

[0463] [Table 1]

[0464] As shown in Table 1, it was found that the rare earth complex (1a) of the present invention has high acid resistance by introducing a specific ligand. [Industrial applicability]

[0465] The rare earth complex (1a) of the present invention is excitable with blue light and has excellent acid resistance. Therefore, it is useful as a light-emitting material for solar cell films, agricultural films, LED phosphors, and security inks, as well as a wavelength conversion material used in them.

Claims

1. A rare earth complex represented by general formula (1a). 【Chemistry 1】 {In the formula, R Ａ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a naphthyl group, anthryl group, a thienyl group, or a furanyl group. These groups, excluding linear, branched, or cyclic haloalkyl groups, may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyloxy group having 1 to 3 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a methylenedioxy group, an ethylenedioxy group, a halogen atom, a hydroxyl group, a nitro group, and a cyano group. Ａ This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b). 【Chemistry 2】 [In the formula, R １ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a heteroaryl group having 4 to 18 carbon atoms. These groups may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. １ This represents an optional amino group shown by the following general formula (Z1). 【Transformation 3】 (wherein, R Ｚ１ and R Ｙ１ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 14 carbon atoms, and the linear, branched or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group and a nitro group. Further, R Ｚ１ and R Ｙ１ may form a ring together with the nitrogen atom to which they are attached.) Further, R １ represents an optionally substituted oxy group represented by the following general formula (Y1). 【Chemistry 4】 (In the formula, R Ｘ１ (These are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms. The linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group.) 【Transformation 5】 [In the formula, R ２ This represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, a heteroaryl group having 4 to 18 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, or a nitro group. Also, R ２ This represents an optional amino group shown by the general formula (Z2) below. 【Transformation 6】 (In the formula, R Ｚ２ and R Ｙ２ Each of these is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and the linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Ｚ２ and R Ｙ２ (It may also form a ring with the bonded nitrogen atom.) Multiple R ２ These may be the same or different. Also, two adjacent R ２ It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R Ｂ R represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a cyano group, or a nitro group. Ｂ They may be the same or different. Also, two adjacent R Ｂ It may also form a ring by being integrated with the bonded benzene ring. In the formula, m １ is 1 or 2, m ２ It is 0. In the ceremony, L １ This represents triphenylphosphine oxide, tricyclohexylphosphine oxide, tri(o-tolyl)phosphine oxide, dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine oxide, 1,8-bis(diphenylphosphino)naphthalene, bis[2-[(oxo)diphenylphosphino]phenyl] ether, 1,10-phenanthroline, dipyrido[3,2-a:2',3'-c]phenazine, or 2,2'-bipyridyl. １ When is an integer of 2, multiple L １ They may be the same or different. In the ceremony, L ２ This represents water. In the formula, M represents the europium ion. In the formula, X Ｌ This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or a β-diketnate ion having 5 to 12 carbon atoms. In the equation, n is 0.

2. R Ｂ The rare earth complex according to claim 1, wherein is a hydrogen atom.

3. In the above general formula (2a), R １ The rare earth complex according to claim 1 or 2, wherein the group comprises a linear, branched, or cyclic alkyloxy group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a phenothiazinyl group, a xanthenyl group, a phenoxazinyl group, a carbazoyl group, or a diphenylamino group (excluding the linear, branched, or cyclic alkyloxy group having 1 to 4 carbon atoms and the linear, branched, or cyclic dialkylamino group having 2 to 8 carbon atoms, these groups may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic fluoroalkyl group having 1 to 4 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 5 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group).

4. In the general formula (2b) above, E is an oxygen atom, and R ２ The rare earth complex according to any one of claims 1 to 3, wherein the group comprises a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 4 carbon atoms, a diphenylamino group, a phenoxy group, a linear, branched, or cyclic alkylcarbonyl group having 2 to 5 carbon atoms, a cyano group, or a nitro group.

5. R in the general formula (2b) ２ The rare earth complex according to claim 4, wherein the complex is a hydrogen atom, a linear, branched, or cyclic alkyloxy group having 1 to 4 carbon atoms, or a nitro group.

6. A rare earth complex according to any one of claims 1 to 5, which is a complex represented by any one of the formulas (1a-1), (1a-2), (1a-4) to (1a-8), (1a-10) to (1a-14), (1a-22), (1a-28), (1a-34), (1a-35), (1a-37), and (1a-44). 【Transformation 7】

7. An enol represented by the following general formula (4a) and one of the following L: triphenylphosphine oxide, tricyclohexylphosphine oxide, tri(o-tolyl)phosphine oxide, dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine oxide, 1,8-bis(diphenylphosphinyl)naphthalene, bis[2-[(oxo)diphenylphosphino]phenyl] ether, 1,10-phenanthroline, dipyrido[3,2-a:2',3'-c]phenazine, and 2,2'-bipyridyl １ A method for producing a rare earth complex according to any one of claims 1 to 6, characterized by reacting with a europium compound. 【Transformation 8】 {In the formula, R Ａ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a naphthyl group, anthryl group, a thienyl group, or a furanyl group. These groups, excluding linear, branched, or cyclic haloalkyl groups, may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyloxy group having 1 to 3 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a methylenedioxy group, an ethylenedioxy group, a halogen atom, a hydroxyl group, a nitro group, and a cyano group. Ａ This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b). 【Chemistry 9】 [In the formula, R １ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a heteroaryl group having 4 to 18 carbon atoms. These groups may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. １ This represents an optional amino group shown by the following general formula (Z1). 【Chemistry 10】 (In the formula, R Ｚ１ and R Ｙ１ Each of these is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and the linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Ｚ１ and R Ｙ１ It may form a ring together with the bonded nitrogen atom. Also, R １ This represents a substituted oxy group shown by the following general formula (Y1). 【Chemistry 11】 (In the formula, R Ｘ１ (These are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms. The linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group.) 【Chemistry 12】 [In the formula, R ２ This represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, a heteroaryl group having 4 to 18 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, or a nitro group. Also, R ２ This represents an optional amino group shown by the general formula (Z2) below. 【Chemistry 13】 (In the formula, R Ｚ２ and R Ｙ２ Each of these is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and the linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Ｚ２ and R Ｙ２ (It may also form a ring with the bonded nitrogen atom.) Multiple R ２ These may be the same or different. Also, two adjacent R ２ It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R Ｂ R represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a cyano group, or a nitro group. Ｂ They may be the same or different. Also, two adjacent R Ｂ It may form a ring by being integrated with the bonded benzene ring.

8. A diketonate complex represented by the following general formula (1aq) and L, which is one of the following: triphenylphosphine oxide, tricyclohexylphosphine oxide, tri(o-tolyl)phosphine oxide, dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine oxide, 1,8-bis(diphenylphosphinyl)naphthalene, bis[2-[(oxo)diphenylphosphino]phenyl]ether, 1,10-phenanthroline, dipyrido[3,2-a:2',3'-c]phenazine, and 2,2'-bipyridyl １ A method for producing a rare earth complex according to any one of claims 1 to 6, characterized by reacting with 【Chemistry 14】 {In the formula, R Ａ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a naphthyl group, anthryl group, a thienyl group, or a furanyl group. These groups, excluding linear, branched, or cyclic haloalkyl groups, may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyl group having 1 to 3 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 3 carbon atoms, a linear, branched, or cyclic fluoroalkyloxy group having 1 to 3 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a methylenedioxy group, an ethylenedioxy group, a halogen atom, a hydroxyl group, a nitro group, and a cyano group. Ａ This represents an aryl group represented by the following general formula (2a) or a heteroaryl group represented by the following general formula (2b). 【Chemistry 15】 (In the formula, R １ R represents a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a heteroaryl group having 4 to 18 carbon atoms. These groups may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. １ This represents an optional amino group shown by the following general formula (Z1). 【Chemistry 16】 (In the formula, R Ｚ１ and R Ｙ１ Each of these is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and the linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Ｚ１ and R Ｙ１ It may form a ring together with the bonded nitrogen atom. Also, R １ This represents a substituted oxy group shown by the following general formula (Y1). 【Chemistry 17】 (In the formula, R Ｘ１ (These are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms. The linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group.) [Chemistry 18] [In the formula, R ２ This represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, a heteroaryl group having 4 to 18 carbon atoms, an aryloxy group having 5 to 14 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, or a nitro group. Also, R ２ This represents an optional amino group shown by the general formula (Z2) below. 【Chemistry 19】 (In the formula, R Ｚ２ and R Ｙ２ Each of these is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and the linear, branched, or cyclic alkyl group or aryl group may be substituted with one or more substituents selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, a cyano group, and a nitro group. Ｚ２ and R Ｙ２ (It may also form a ring with the bonded nitrogen atom.) Multiple R ２ These may be the same or different. Also, two adjacent R ２ It may also form a ring by being integrated with the bonded benzene ring. In the formula, E represents an oxygen atom, a sulfur atom, or a nitrogen atom. The nitrogen atom may be substituted with a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, or a linear, branched, or cyclic alkylcarbonyl group having 2 to 7 carbon atoms. In the formula, R Ｂ R represents a hydrogen atom, a deuterium atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a linear, branched, or cyclic haloalkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic monoalkylamino group having 1 to 6 carbon atoms, a monoarylamino group having 5 to 12 carbon atoms, a linear, branched, or cyclic dialkylamino group having 2 to 12 carbon atoms, a diarylamino group having 10 to 24 carbon atoms, a cyano group, or a nitro group. Ｂ They may be the same or different. Also, two adjacent R Ｂ It may form a ring by being integrated with the bonded benzene ring. In the formula, m represents an integer of 0, 1, 2, or 3. In the formula, Q １ This represents water. In the formula, M represents the europium ion. In the formula, X Ｌ This represents a halide ion, nitrate ion, carboxylate ion, sulfonate ion, or a β-diketnate ion having 5 to 12 carbon atoms. In the formula, n represents 0.

9. An optical material comprising the rare earth complex (1a) described in any one of claims 1 to 6.

10. Furthermore, the optical material according to claim 9 further comprises a resin material, inorganic glass, organic low molecular weight material, or solvent.

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 and copolymers thereof; epoxy resin; polyimide resin; or silicon resin.

12. The optical material according to claim 9, wherein the solvent according to claim 10 is halogenated hydrocarbons, alcohols, esters, glycol ethers, ethers, ketones, or hydrocarbons.

13. The optical material according to any one of claims 10 to 12, which is a film for solar cells, an agricultural film, an LED phosphor, a light-emitting material, a fluorescent material, or a wavelength conversion material.

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