Circularly polarized luminescent rare earth complex, coating composition, molded article, film, optical functional material, three-dimensional display, method for producing circularly polarized luminescent rare earth complex, and use of circularly polarized luminescent rare earth complex

Abstract

To provide a circularly polarized luminescent rare earth complex, a coating composition, a molded article, an optical functional material, a three-dimensional display, a method for producing the circularly polarized luminescent rare earth complex, and a use of the circularly polarized luminescent rare earth complex, which are excellent in luminescence quantum efficiency.SOLUTION: The circularly polarized luminescent rare earth complex is represented by the following General Formula (1) or (2), or each enantiomer thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a circularly polarized luminescent rare earth complex, a coating composition containing the circularly polarized luminescent rare earth complex, a molded article or film containing the circularly polarized luminescent rare earth complex, an optical functional material containing the circularly polarized luminescent rare earth complex, a three-dimensional display having the optical functional material, a method for producing the circularly polarized luminescent rare earth complex, and use of the circularly polarized luminescent rare earth complex. [Background technology]

[0002] In recent years, it has been expected that optical functional materials that exhibit circularly polarized luminescence will be applied to three-dimensional displays and electronic paper by combining them with organic electroluminescent devices. Optical functional materials that exhibit circularly polarized luminescence are also attracting attention as raw materials for security markers and invisible inks, as they can add right- and left-handed circularly polarized light to ordinary visible light as security information. Furthermore, it has been reported that these materials have the effect of accelerating plant growth and improving the conversion efficiency of solar cells, and there is growing interest in materials that convert natural light into circularly polarized light.

[0003] One such optically functional material is a rare earth complex. For example, rare earth complexes in which both a binaphthyl structure ligand, such as BINAPO (1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine oxide)), and a facam (3-trifluoroacetyl-D-camphorate) derivative are coordinated to a rare earth ion, and rare earth complexes in which both a phosphine oxide derivative, such as TPPO (triphenylphosphine oxide 10 e), and a facam derivative are coordinated to a rare earth ion have been reported (see Patent Documents 1 to 3). These rare earth complexes are known to selectively emit right-handed and left-handed circularly polarized light due to the asymmetric ligand field resulting from the optically active structures of the binaphthyl structure ligand, facam derivative, and phosphine oxide derivative, i.e., to possess circularly polarized luminescence.

[0004] Patent Document 4 discloses a polymeric rare earth complex having a phosphine oxide dentate ligand in the linking chain. This polymeric rare earth complex contains two types of ligands with different structures as non-linking ligands, and achieves both long-wavelength excitation and heat resistance.

[0005] Patent Document 5 discloses a circularly polarized luminescent rare earth complex represented by general formula (1) or its enantiomer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-327590 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-097240 [Patent Document 3] International Publication No. 2008 / 111293 [Patent Document 4] Japanese Patent Application Publication No. 2019-127560 [Patent Document 5] Japanese Patent Application Publication No. 2020-121928 Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Document 4 describes a polymeric rare earth complex, but does not disclose that it exhibits any particular effect in terms of light-emitting properties. The circularly polarized luminescent rare earth complex of Patent Document 5 has a circular polarization property of 0.04 to 1.5 and a luminescence quantum efficiency of 7 to 11%, which is low.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a circularly polarized luminescent rare earth complex having excellent luminescence quantum efficiency, a coating composition, a molded product, a film, an optically functional material, a three-dimensional display, a method for producing a circularly polarized luminescent rare earth complex, and use of the circularly polarized luminescent rare earth complex. [Means for solving the problem]

[0009] The present invention has the following aspects. [1] A circularly polarized luminescent rare earth complex represented by the following general formula (1) or (2), or an enantiomer thereof:

[0010] [ka] (In general formula (1), Ln 3+ represents a trivalent rare earth ion. Each Z independently represents phosphine oxide (P=O) or phosphorus (P). Each Y independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, and for each phenyl group to which Y is bonded, at least one Y in the ortho position relative to Z is an alkoxy group, an ester group, or an acyloxy group, and each hydrogen atom in the hydrocarbon that may be contained in Y may be independently substituted with a halogen atom. X represents a direct bond, or -O-, -S-, -NR- (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms), or a hydrocarbon group having 1 carbon atom. Each Q independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, or may be bonded to each other to form a 6-membered aromatic hydrocarbon ring, and each hydrogen atom in the hydrocarbon that may be included in Q may be independently substituted with a halogen atom. R 1 represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. R 2 and R 3each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R 2 and R 3 Each hydrogen atom in the hydrocarbon that may be contained in may be independently substituted with a halogen atom. n1 represents a natural number from 0 to 6, n2 represents a natural number from 0 to 3, and n1 + 2 × n2 is 0 to 6. m represents a natural number from 1 to 4. When n1 or n2 is 2 or more, the structures in parentheses may be the same or different. A + represents a monovalent cation, and m2 represents 0 or 1.

[0011] [ka] (In general formula (2), R 1 ,R 2 ,R 3 Y and Z are as defined in the general formula (1), LL is a linker ligand coordinated to two or more of the rare earth ions, m is 1 to 3, and n1 is 0 to 4. + represents a monovalent cation, and m3 represents 0 or 1.

[0012] [2] The circularly polarized luminescent rare earth complex according to [1], wherein the main chain of the general formula (2) contains one phosphoryl group represented by the following general formula (3) at an end of the main chain:

[0013] [ka] (In general formula (3), Ln 3+ , R 1 ,R 2 ,R 3 Y and Z are the same as those in the general formula (1), LL is a linker ligand coordinated to two or more of the rare earth ions, m is 1 to 3, and n1 is 0 to 4. 3+may be the same or different. A + represents a monovalent cation, and m3 represents 0 or 1.

[0014] [3] The circularly polarized luminescent rare earth complex according to [1] or [2], wherein the absolute configuration of the ligand around the rare earth ion is at least one of a right-handed helical Δ configuration and a left-handed helical Λ configuration.

[0015] [4] A coating composition comprising the circularly polarized luminescent rare earth complex according to any one of [1] to [3].

[0016] [5] A molded article or film comprising the circularly polarized luminescent rare earth complex according to any one of [1] to [3].

[0017] [6] An optically functional material comprising the circularly polarized luminescent rare earth complex according to any one of [1] to [3].

[0018] [7] A three-dimensional display having the optically functional material according to [6].

[0019] [8] A camphor derivative represented by the following general formula (4) and a monovalent cation A + preparing a solution containing a salt consisting of: adding a solution containing rare earth ions to the solution to react the camphor derivative with the rare earth ions to obtain a reaction product; and washing the reaction product with a solvent and then drying the same. R of the camphor derivative 1 The method for producing a circularly polarized luminescent rare earth complex is to obtain at least one of a right-handed helical Δ form and a left-handed helical Λ form in which the absolute configuration of the ligand around the rare earth ion is at least one of a right-handed helical Δ form and a left-handed helical Λ form by making the structure of the compound (I) a sterically bulky structure or a structure having a substituent, or by adding an optically active substance to the reaction solution.

[0020] [ka] (In general formula (4), R 1represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. R 2 and R 3 each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R 2 and R 3 Each hydrogen atom in the hydrocarbon may be independently substituted with a halogen atom.

[0021] [9] Use of a circularly polarized luminescent rare earth complex, wherein the circularly polarized luminescent rare earth complex according to any one of [1] to [3] is used at a temperature of -200°C or higher and 200°C or lower. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a circularly polarized luminescent rare earth complex having excellent luminescence quantum efficiency, a coating composition, a molded product, a film, an optically functional material, a three-dimensional display, a method for producing a circularly polarized luminescent rare earth complex, and a use of the circularly polarized luminescent rare earth complex. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 2 is a diagram showing the results of measuring the emission spectra of circularly polarized luminescent rare earth complexes in Examples and Comparative Examples. [Figure 2] FIG. 1 is a diagram showing the results of measuring the luminescence decay behavior of circularly polarized luminescent rare earth complexes of Examples and Comparative Examples. [Figure 3] FIG. 1 is a diagram showing the results of measuring the circularly polarized luminescence (CPL) spectrum of the circularly polarized luminescent rare earth complex of Example 1. [Figure 4] FIG. 2 is a graph showing the results of measuring the temperature dependence of the circularly polarized luminescence of the circularly polarized luminescent rare earth complex of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments and examples of the present disclosure will be described with reference to the drawings, etc. However, the present disclosure can be implemented in many different forms, and should not be construed as being limited to the description of the embodiments and examples exemplified below. Furthermore, to clarify the explanation, the drawings may show the width, thickness, shape, etc. of each part more schematically than the actual form, but these are merely examples and do not limit the interpretation of the present disclosure. In addition, in this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit.

[0025] [Circularly polarized luminescent rare earth complexes] The present disclosure provides a circularly polarized luminescent rare earth complex represented by the following general formula (1) or (2), or an enantiomer thereof:

[0026] [ka] (In general formula (1), Ln 3+ represents a trivalent rare earth ion. Each Z independently represents phosphine oxide (P=O) or phosphorus (P). Each Y independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, and for each phenyl group to which Y is bonded, at least one Y in the ortho position relative to Z is an alkoxy group, an ester group, or an acyloxy group, and each hydrogen atom in the hydrocarbon that may be contained in Y may be independently substituted with a halogen atom. X represents a direct bond, or -O-, -S-, -NR- (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms), or a hydrocarbon group having 1 carbon atom. Each Q independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, or may be bonded to each other to form a 6-membered aromatic hydrocarbon ring, and each hydrogen atom in the hydrocarbon that may be included in Q may be independently substituted with a halogen atom. R 1 represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. R 2 and R 3 each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R 2 and R 3 Each hydrogen atom in the hydrocarbon that may be contained in may be independently substituted with a halogen atom. n1 represents a natural number from 0 to 6, n2 represents a natural number from 0 to 3, and n1 + 2 × n2 is 0 to 6. m represents a natural number from 1 to 4. When n1 or n2 is 2 or more, the structures in parentheses may be the same or different. A + represents a monovalent cation, and m2 represents 0 or 1.

[0027] [ka] (In general formula (2), R 1 ,R 2 ,R 3 Y and Z are as defined in the general formula (1), LL is a linker ligand coordinated to two or more of the rare earth ions, m is 1 to 3, and n1 is 0 to 4. + represents a monovalent cation, and m3 represents 0 or 1.

[0028] The circularly polarized luminescent rare earth complex of the present disclosure can form a film with high luminescence intensity, excellent circularly polarized luminescence, and excellent transparency. In the circularly polarized luminescent rare earth complex of the present disclosure, the absolute configuration of the ligand around the rare earth ion is at least one of a right-handed helical Δ configuration and a left-handed helical Λ configuration.

[0029] The circularly polarized luminescent rare earth complex of the present disclosure has one to four chiral ligands (i) having an asymmetric carbon atom, and at least one of ligands (ii-1) and (ii-2). In ligands (ii-1) and (ii-2), at least one Y is an alkoxy group, ester group, acyloxy group, hydroxyl group, nitro group, amino group, sulfonyl group, cyano group, silyl group, phosphonic acid group, diazo group, or mercapto group per phenyl group bonded to phosphine oxide (P═O) or phosphorus (P) coordinated to a rare earth ion, and has a bulky substituent. The presence of the bulky substituent results in the circularly polarized luminescent rare earth complex represented by general formula (1) or its enantiomer having multiple stable complex structures, making it amorphous and forming an optically isotropic system. It is therefore presumed that this leads to high transparency even when the complex is used alone to form a film. Furthermore, due to the appropriate steric hindrance caused by the introduction of the bulky substituent, the coordination distance of the ligands (ii-1) and (ii-2) to at least one rare earth ion increases, while the coordination distance of the three chiral ligands (i) to the rare earth ion decreases. This presumably enhances the chiral effect of the specific circularly polarized luminescent rare earth complex, resulting in excellent circularly polarized luminescence. Furthermore, the substituent has a weak coordination ability to the rare earth central metal, which causes interactions between the complex molecules and increases the amorphousness of the aggregate. This presumably contributes to the excellent transparency of the specific circularly polarized luminescent rare earth complex when made into a film. Furthermore, because the ligand (i) has a β-diketone structure and a high extinction coefficient, it can efficiently supply the energy of excitation light to the coordinated rare earth ion. The introduction of bulky substituents into the ligands (ii-1) and (ii-2) as a whole results in appropriate steric hindrance, which shortens the coordination distance of the three chiral ligands (i) to the rare earth ion, thereby enabling the excitation light energy to be efficiently supplied to the rare earth ion and improving the overall luminescence intensity. It is therefore presumed that the specific circularly polarized luminescent rare earth complex exhibits increased luminescence intensity at the emission wavelength with the maximum g value.

[0030] In the general formula (1), Ln 3+ represents a trivalent rare earth ion, specifically, Eu 3+ , Tb3+ , Sm 3+ , Er 3+ , Pr 3+ , Ho 3+ , Tm 3+ and Dy 3+ The trivalent rare earth ion is selected appropriately so as to obtain a desired luminescent color, and among them, Eu is preferred because it has excellent luminous efficiency and high luminous intensity. 3+ or Tb 3+ is preferred, and Eu 3+ is more preferred.

[0031] In the general formula (1), each Z independently represents phosphine oxide (P=O) or phosphorus (P), and may be either of them. Among them, phosphine oxide is preferred because it has a low vibration structure and can improve the emission intensity.

[0032] In the general formula (1), each Y independently represents a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group, and for each phenyl group to which a Y is bonded, at least one Y is an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0033] Hydrocarbons that may be contained in Y, specifically, the alkoxy group (-OR a ), ester group (-COOR b ), acyloxy group (-OCOR c ), amino group (-NR d R e ), sulfonyl group (-SO2R f ), silyl group (-SiR g R h R i ) (where R a , R b , R c , Rf each independently represents a hydrocarbon group, R d , R e , R g , R h , R i each independently represents a hydrogen atom or a hydrocarbon group), the hydrocarbon that may be contained therein may each independently be a hydrocarbon group having 1 to 22 carbon atoms.

[0034] In the hydrocarbon group having 1 to 22 carbon atoms, the hydrocarbon may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may be a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 4 carbon atoms. Furthermore, each hydrogen atom in the hydrocarbon that may be contained in Y may be independently substituted with a halogen atom.

[0035] For each phenyl group to which Y is bonded, at least one Y is an alkoxy group, ester group, acyloxy group, hydroxyl group, nitro group, amino group, sulfonyl group, cyano group, silyl group, phosphonic acid group, diazo group, or mercapto group. From the viewpoint of increasing circularly polarized luminescence, it is preferable that at least one Y at the ortho or meta position relative to Z is an alkoxy group, ester group, acyloxy group, hydroxyl group, nitro group, amino group, sulfonyl group, cyano group, silyl group, phosphonic acid group, diazo group, or mercapto group, and it is more preferable that at least one Y at the ortho position relative to Z is an alkoxy group, ester group, acyloxy group, hydroxyl group, nitro group, amino group, sulfonyl group, cyano group, silyl group, phosphonic acid group, diazo group, or mercapto group.

[0036] X represents a direct bond, or -O-, -S-, -NR- (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms), or a hydrocarbon group having 1 to 22 carbon atoms. When X is a direct bond, X does not contain a divalent group and represents a structure in which phenylene groups are directly bonded to each other. The hydrocarbon group having 1 to 22 carbon atoms in -NR- may be the same as the hydrocarbon group having 1 to 22 carbon atoms in Y. The hydrocarbon group having 1 to 22 carbon atoms in X represents a divalent hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon may also be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group having 1 to 22 carbon atoms in X may be a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 4 carbon atoms.

[0037] Each Q independently represents a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group, or may bond to each other to form a 6-membered aromatic hydrocarbon ring, and each hydrogen atom in the hydrocarbon that may be contained in Q may be independently substituted with a halogen atom. The halogen atom, alkoxy group, ester group, acyloxy group, amino group, sulfonyl group, and silyl group in Q may each be the same as those in Y. Each Q may bond to each other to form a 6-membered aromatic hydrocarbon ring, and the 6-membered aromatic hydrocarbon ring may be fused with the phenylene group to which it is bonded.

[0038] R 1 represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. Examples of the aromatic group having 6 to 22 carbon atoms which may have a substituent include monovalent aromatic groups such as a phenyl group, a naphthyl group, anthracene, phenanthrene, chrysene, and pyrene. Examples of heteroaromatic groups include monovalent heteroaromatic groups such as furanyl, thienyl, pyrrole, pyridyl, imidazolyl, triazolyl, benzofuranyl, benzothienyl, indolyl, quinolyl, carbazolyl, acridine, xanthene, coumarin, and benzimidazole. These aromatic or heteroaromatic groups may have at least one or more substituents, and the substituents may be any of alkyl groups, aromatic groups, heteroaromatic groups, alkoxy groups, ester groups, acyloxy groups, hydroxyl groups, nitro groups, amino groups, sulfonyl groups, cyano groups, silyl groups, phosphonic acid groups, diazo groups, mercapto groups, halogen atoms, and halogenated alkyl groups. 1 However, by using any one of the above groups, the carbon atom directly bonded to the oxygen atom coordinated to the rare earth ion is less likely to vibrate, and a decrease in the luminescence intensity of the rare earth complex can be suppressed.

[0039] R 2 and R 3 each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R 2 and R 3 Each hydrogen atom in the hydrocarbon that may be contained in may be independently substituted with a halogen atom.

[0040] n1 is the coordination number of the monodentate ligand (ii-1) and represents a natural number from 0 to 6, n2 is the coordination number of the bidentate ligand (ii-2) and represents a natural number from 0 to 3. Furthermore, m represents the coordination number of the bidentate ligand (i) and represents a natural number from 1 to 4. The coordination number of the rare earth complex represented by the general formula (1) can be 7 to 12 in total, so n1+2×n2+2×m is 7 or more and 12 or less, and therefore n1+2×n2 is 0 or more and 6 or less. The coordination number of the rare earth complex represented by the general formula (1) is preferably 7 to 9 in total, and n1+2×n2+2×m is preferably 7 or more and 9 or less, and therefore n1+2×n2 is preferably 1 or more and 3 or less.

[0041] A + represents a monovalent cation. + Li + , Na + , K. + , Rb + , Cs + , ammonium cation, phosphonium cation, sulfonium cation, oxonium cation, iodonium cation, pyridinium cation, imidazolinium cation, diazonium cation, pyrilinium cation, chromenium cation, isochromenium cation, pyrrolidinium cation, amidinium cation, morpholinium cation, pyridinium cation, quinolium cation, isoquinolium cation, acridium cation, guanidinium cation, sulfoxonium cation, thianthrenium cation, or thiophenium cation. The monovalent cation is appropriately selected so as to obtain a desired luminescent color, and among these, from the viewpoints of excellent circularly polarized luminescence characteristics and high luminescent intensity, monovalent cations of alkali metals or ammonium cations are preferred, and ammonium cations are more preferred. Examples of ammonium cations include n-butylammonium cation, diethylammonium cation, trimethylammonium cation, tetraethylammonium cation, triethylmethylammonium cation, phenyltrimethylammonium cation, and tetrabutylammonium cation. m2 represents 0 or 1, and when m=0 to 3, m2=0, and when m=4, m=1.

[0042] The main chain of the rare earth complex polymer represented by general formula (2) can contain one or more linker ligands. The linker ligand (e.g., LL in formula (2)) usually has two groups that coordinate to the rare earth ion. The linker ligand may be a compound having two phosphoryl groups (>P(=O)-). The linker ligand having two phosphoryl groups may be a compound represented by the following formula (20).

[0043] [ka]

[0044] In formula (20), Ar 2 represents a monovalent aromatic group which may have a substituent, and two Ar 2 may be bonded directly or via a divalent organic group. L represents a divalent organic group.

[0045] Ar 2 may be a phenyl group which may have a substituent. The substituent may be a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group. 2 When is bonded via a divalent organic group, the divalent organic group may be an alkylene group, an arylene group, or a carbonyl group.

[0046] The divalent organic group represented by L may be, for example, a divalent saturated or unsaturated aliphatic group, a divalent aromatic group, or an oxyalkylene group, each of which may have a substituent. Examples of the divalent unsaturated aliphatic group include alkylene groups such as vinylene groups. Examples of the oxyalkylene group include oxymethylene groups.

[0047] The divalent aromatic group represented by L can be a monocyclic ring, a fused polycyclic ring, or a group containing a combination thereof. Examples of monocyclic rings include a benzene ring, a thiophene ring, and a pyridine ring. Examples of groups containing a combination of monocyclic rings include a biphenylene group. Specific examples of L include groups represented by the following formulas (30a), (30b), (30c), and (30d).

[0048] [ka]

[0049] In these formulas, R 30 represents a hydrogen atom or a monovalent substituent, and multiple R 30 may be the same or different. 3 represents a hydrogen atom or an aromatic group (e.g., a phenyl group) which may have a substituent. n is 1 or 2. R 30 The monovalent substituent as may be a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group.

[0050] The linker ligand may be one or more bidentate ligands selected from dpb, dpbp, dpt, and dpf of the formula:

[0051] [ka]

[0052] The main chain of the rare earth complex polymer may further contain a monodentate terminal ligand coordinated to a rare earth ion located at its terminal. In this case, the main chain of the rare earth complex polymer may contain one type of non-linker ligand, or may contain two or more types of non-linker ligands. The terminal ligand is a ligand different from the non-linker ligand. Here, "a rare earth ion located at the terminal of the main chain" means the rare earth ion located at the most terminal of the multiple rare earth ions contained in the main chain.

[0053] By introducing a terminal ligand into the end of the main chain of a rare earth complex polymer, various properties such as excitation by long-wavelength excitation light, heat resistance, and thermosensitive luminescence can be improved to high levels that were difficult to achieve with linker ligands and non-linker ligands alone.

[0054] The terminal ligand can be, for example, a compound having one phosphoryl group. The terminal ligand having one phosphoryl group may be, for example, a compound represented by the following formula (50).

[0055] [ka]

[0056] In the formula, Y has the same meaning as in general formula (1). By introducing the terminal ligand of formula (50), for example, the temperature region in which the rare earth complex polymer exhibits thermosensitive luminescence tends to shift to a higher temperature side compared with a rare earth complex polymer that does not contain a terminal ligand.

[0057] When the rare earth complex polymer containing the terminal ligand of formula (50) contains a constitutional unit represented by the above formula (2), the main chain of the rare earth complex polymer may contain a constitutional unit represented by the above general formula (3) containing the terminal ligand of formula (50).

[0058] The proportion of the terminal ligands contained in the rare earth complex polymer can be determined depending on the desired properties, etc. For example, the proportion of the terminal ligands relative to the total amount of the linker ligands and the terminal ligands may be 1 to 50 mol %.

[0059] The circularly polarized luminescent rare earth complex can be synthesized, for example, by stirring a rare earth metal compound, which is a raw material for rare earth ions, and a compound to be a ligand, in a solvent that can dissolve or disperse them, optionally in the presence of a catalyst. As the solvent, a mixture of solvents suitable for the rare earth metal compound and the compound to be a ligand may be used, for example, a mixed solvent of water / methanol.

[0060] The circularly polarized luminescent rare earth complex according to the present disclosure has a luminescence quantum efficiency superior to that of conventional circularly polarized luminescent rare earth complexes. By absorbing one type of circularly polarized light into the circularly polarized luminescent rare earth complex according to the present disclosure, the other type of circularly polarized light can be obtained. Because the circularly polarized luminescent rare earth complex according to the present disclosure functions in the same way as a circularly polarizing filter such as a circular polarizer, it is possible to apply the circularly polarized luminescent rare earth complex according to the present disclosure to a circularly polarizing filter. This circularly polarizing filter can be used in a wide range of applications, such as optical multiplex communications.

[0061] In the circularly polarized luminescent rare earth complex according to the present disclosure, by synthesizing the complex using separate ligands that differ only in optical rotation, it is possible to obtain both complexes that strongly absorb left-handed circularly polarized light and those that strongly absorb right-handed circularly polarized light, even with the same composition. Furthermore, even within a single circularly polarized luminescent rare earth complex, there are cases where the complex strongly absorbs left-handed circularly polarized light and those that strongly absorb right-handed circularly polarized light, depending on the wavelength. Therefore, by defining one property as "+1" and one having the other property as "-1," information can be recorded by arranging this complex or an optically functional material containing this complex, and the information can be read by irradiating it with circularly polarized light. When the circularly polarized luminescent rare earth complex according to the present disclosure is applied to security applications, it can retain three pieces of information: luminescence upon excitation, circular polarization, and color change due to temperature, thereby enabling simple and advanced security to be achieved.

[0062] The circularly polarized luminescent rare earth complex according to the present disclosure has the properties of a phosphor, and the wavelength at which the luminescence intensity is maximized is not particularly limited, but is usually 300 nm or more and 1600 nm or less. In terms of circularly polarized luminescence, the circularly polarized luminescent rare earth complex according to the present disclosure has a g measured using a circularly polarized luminescence spectrum in the same manner as in the examples described below. CPL The absolute value of the value is preferably 0.04 or more, more preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The circularly polarized luminescent rare earth complex according to the present disclosure has a gCPL It is preferable that the luminous efficiency is high because the luminous intensity at the luminous wavelength with the maximum value is high and the detection level of circularly polarized luminescence is increased. The luminous efficiency is preferably 1% or more, and more preferably 5% or more.

[0063] Furthermore, in order to improve the detection level of circularly polarized luminescence by having the circularly polarized luminescent rare earth complex present at a high concentration in the film, the circularly polarized luminescent rare earth complex preferably has low crystallinity and high transparency when formed into a film alone. For this reason, the circularly polarized luminescent rare earth complex according to the present disclosure preferably has a total light transmittance of 85% or more, more preferably 90% or more, when formed into a film alone with a thickness of 200 μm.

[0064] The circularly polarized luminescent rare earth complex according to the present disclosure preferably has a maximum value in the range of 350 nm or more and 400 nm or less in the excitation spectrum, which is obtained by measuring the luminescence intensity by scanning the wavelength of excitation light, with the maximum emission wavelength in the emission spectrum being the detection wavelength, from the viewpoint of enabling detection of circularly polarized luminescence using a commonly available ultraviolet light source for excitation irradiation. The circularly polarized luminescent rare earth complexes of the present disclosure may be used singly or in combination of two or more, and may be mixed with an organic dye to change the luminescent color.

[0065] [Method for producing circularly polarized luminescent rare earth complexes] The present disclosure relates to a camphor derivative represented by the following general formula (3) and a monovalent cation A + (hereinafter referred to as "first step"), a step of adding a solution containing rare earth ions to the above solution to react the camphor derivative with the rare earth ions to obtain a reaction product (hereinafter referred to as "second step"), and a step of washing the reaction product with a solvent and then drying it (hereinafter referred to as "third step"), 1 The present invention provides a method for producing a circularly polarized luminescent rare earth complex, which produces at least one of a Δ form and a Λ form by converting the structure of the compound (I) into a sterically bulky structure or a structure having a substituent, or by adding an optically active substance to the reaction solution.

[0066] [ka] (In general formula (4), R 1 represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. R 2 and R 3 each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R 2 and R 3 Each hydrogen atom in the hydrocarbon may be independently substituted with a halogen atom.

[0067] The first step is to react a camphor derivative represented by the following general formula (4) with a monovalent cation A + The solution is prepared by dissolving the camphor derivative represented by the following general formula (4) and a monovalent cation A in a solvent. + The salt consisting of the above is added and stirred to mix.

[0068] Examples of the solvent that can be used include alcohols such as methanol and ethanol, halogen-based solvents such as methylene chloride and chloroform, and ether-based solvents.

[0069] The second step is a step of adding a solution containing rare earth ions to the above solution to react the camphor derivative with the rare earth ions, thereby obtaining a reaction product.

[0070] The solution containing rare earth ions is obtained by dissolving a salt containing rare earth ions in a solvent. As the solvent, for example, the same solvent as in the first step can be used. Salts containing rare earth ions include Eu 3+, Tb 3+ , Sm 3+ , Er 3+ , Pr 3+ , Ho 3+ , Tm 3+ and Dy 3+ It is possible to use a salt containing a rare earth ion selected from the group consisting of: Specific examples include chlorides and acetates of rare earth ions.

[0071] The third step is to wash the reaction product with a solvent and then dry it.

[0072] Examples of the solvent used to wash the reaction product include water and alcohol.

[0073] The method for drying the reaction product after washing is not particularly limited, and the reaction product may be dried at room temperature, by heating, or under reduced pressure.

[0074] By going through the first step to the third step, R of the camphor derivative 1 By making the structure of the formula (I) a sterically bulky structure or a structure having a substituent, or by adding an optically active substance to the reaction solution, a circularly polarized luminescent rare earth complex can be obtained in which the absolute configuration of the ligand around the rare earth ion is at least one of a right-handed helix Δ form and a left-handed helix Λ form.

[0075] [Paint composition] The present disclosure provides a coating composition comprising the circularly polarized luminescent rare earth complex according to the present disclosure. The coating composition according to the present disclosure comprises the circularly polarized luminescent rare earth complex according to the present disclosure and a solvent.

[0076] The solvent may be, for example, an alcohol solvent, a ketone solvent, an ester solvent, a nitrile solvent, or a mixture thereof, etc. Preferably, the solvent may be acetonitrile or methanol.

[0077] The coating composition according to the present disclosure may contain a pigment, a binder, a viscosity modifier, etc. As the pigment, a green pigment, a red pigment, or a blue pigment can be used. Examples of green dyes include alkaline earth silicon oxynitride fluorescent materials, fluorescent dyes such as pyridine-phthalimide condensation derivatives, benzoxazinones, quinazolinones, coumarins, quinophthalones, and naltharic acid imides, and organic fluorescent materials such as terbium complexes. Examples of red dyes include phosphors containing oxynitrides with an alpha-sialon structure, and red organic phosphors made of rare earth element ion complexes with anions of β-diketonates, β-diketones, aromatic carboxylic acids, or Bronsted acids as ligands. Examples of blue dyes include alkaline earth aluminate fluorescent materials, fluorescent dyes of naphthalimide, benzoxazole, styryl, coumarin, pyrarizone, and triazole compounds, and organic fluorescent materials such as thulium complexes. The circularly polarized luminescent rare earth complexes according to the present disclosure are generally ionic, and therefore, as the dye to be coexisted with the circularly polarized luminescent rare earth complexes according to the present disclosure, it is preferable to use a nonionic dye composed only of carbon and hydrogen, such as an anthracene-based dye. As the binder, general-purpose resins such as acrylic, ester, amide, urethane, styrene, acetal, carbonate, and vinyl resins can be used.

[0078] As described above, the circularly polarized luminescent rare earth complex according to the present disclosure can retain three pieces of information: luminescence upon excitation, circular polarization, and color change due to temperature, and therefore the coating composition according to the present disclosure can easily achieve a high level of security. In other words, the coating composition according to the present disclosure is preferably a security ink that can display characters, symbols, figures, etc. that retain information.

[0079] [Molded product or film] The present disclosure provides a molded article or film comprising the circularly polarized luminescent rare earth complex according to the present disclosure. The molded article according to the present disclosure comprises the circularly polarized luminescent rare earth complex according to the present disclosure and a transparent polymer in which the circularly polarized luminescent rare earth complex is dispersed.

[0080] Examples of transparent polymers include polyolefins such as polymethyl methacrylate, fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyethylene, polypropylene, and polybutene, fluorine-containing polyolefins, polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, and copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin, and silicone resin, and preferred examples include polymethyl methacrylate, fluorine-containing polymethacrylate, polyacrylate, fluorine-containing polyacrylate, polystyrene, polyolefin, polyvinyl ether, and copolymers thereof, and epoxy resin. These transparent polymers may be used alone or in combination of two or more. The transparent polymer can be prepared according to a known document (Hasegawa, et al. Chem. Lett. 1999, 35.).

[0081] As described above, the circularly polarized luminescent rare earth complex according to the present disclosure can retain three pieces of information: luminescence upon excitation, circular polarization, and color change due to temperature, and therefore the molded article or film according to the present disclosure can easily achieve a high level of security. Specific examples of the molded article or film according to the present disclosure include films for agricultural use, temperature display, etc., and security applications for banknotes, tickets, brand-name goods, etc.

[0082] [Optical functional materials] The present disclosure provides an optically functional material including the circularly polarized luminescent rare earth complex according to the present disclosure. When the circularly polarized luminescent rare earth complex according to the present disclosure is used as an optical functional material, the circularly polarized luminescent rare earth complex according to the present disclosure may be used alone as the optical functional material, or the circularly polarized luminescent rare earth complex according to the present disclosure may be contained in a transparent solid carrier such as a transparent polymer or transparent glass. The circularly polarized luminescent rare earth complex according to the present disclosure emits light in different colors depending on the type of rare earth ion as the central ion and the type of ligand. Therefore, by appropriately selecting the types and mixing ratios of the central ion of the circularly polarized luminescent rare earth complex according to the present disclosure and the organic dyes, optical functional materials that emit light in various colors can be obtained.

[0083] [Three-dimensional display] The present disclosure provides a three-dimensional display having an optically functional material according to the present disclosure. The 3D display according to the present disclosure includes the optical functional material according to the present disclosure as a polarizer. Because the 3D display according to the present disclosure includes the optical functional material according to the present disclosure as a polarizer, it has good color purity and excellent color reproducibility, and is capable of displaying high-brightness, high-resolution images with low power consumption.

[0084] [Use of circularly polarized luminescent rare earth complexes] In the present disclosure, the circularly polarized luminescent rare earth complex according to the present disclosure is used at a temperature of -200°C or higher and 200°C or lower. By using the circularly polarized luminescent rare earth complex according to the present disclosure at a temperature of −200° C. or higher and 200° C. or lower, the circular polarization properties are enhanced. [Example]

[0085] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0086] [Example 1] (Circularly polarized luminescent rare earth complex NEt4 + [Eu(+bzc)4] - Synthesis of (1) Synthesis of (+)-bzc ((+)-bzc; (+)-3-benzoylcamphor) (+)-Benzoylcamphor was synthesized according to the reaction scheme shown below.

[0087] [ka]

[0088] Under an argon atmosphere, NaH (2.52 g, 0.105 mol) was washed with a small amount of hexane, followed by the addition of tetrahydrofuran (ultra-anhydrous, 40 mL) and (+)-camphor (4.13 g, 0.0271 mol) and stirring. The mixture was cooled to 0°C, and ethylbenzoate (4.05 g, 0.0270 mol) was added and stirred for 10 minutes. After returning to room temperature, the mixture was heated to reflux at 70°C for 20 hours. The mixture was cooled again to 0°C, and hydrochloric acid (1 M) was added to adjust the pH to 1-2. The reaction solution was extracted with ethyl acetate and saturated brine, dehydrated over sodium sulfate, and the solvent was evaporated. The resulting residue was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 9 (v / v)). The pink product was recrystallized from pentane to give (+)-benzoylcamphor as pink crystals. Yield: 1.72 g, 25%. 1 H-NMR (400MHz, CDCl3): δ / ppm=7.74-7.69(m,2H),7.42-7.46(m,2.9H),2.84-2.86(d,1H),2.1 2-2.21(m,1H),1.75-1.83(m,1H),1.49-1.66(m,2.2H),1.03(s,3H),0.94(s,3H),0.83(s,3H). 13 C-NMR (100MHz, CDCl3): δ / ppm=213.3,161.8,134.1,130.4,128.4,127.8,115.4,57.7,50.1,48.4,30.6,27.1,20.3,18.8,8.9. IR(ATR):2965(st,CH)cm -1 ,1664(st,C=O)cm -1 ,1593-1610(st,arC=C)cm -1 . ESI-Mass(m / z):[M+H] +calcd.for C 17 H 21 O2,257.15;found,257.15. Elemental analysis(%):calcd.for C 17 H 20 O2,C79.66,H7.86;found,C79.58,H7.92.

[0089] (2) NEt4 + [Eu(+bzc)4] - Synthesis of Next, (+)-BZC (0.400 g, 1.56 mmol) obtained in (1) above and tetraethylammonium chloride (0.184 g, 1.11 mmol) were each dissolved in 10 mL of ethanol. The two solutions were mixed and stirred for approximately 15 minutes. The pH of the mixture was adjusted to 8–9 using 0.5 M NaOH ethanol solution and further stirred for approximately 10 minutes. EuCl3·6H2O (0.215 g, 0.587 mmol) was dissolved in 10 mL of ethanol and added to the mixture. The pH was then adjusted to 8–9 and the mixture was heated under reflux for 4 hours. The precipitate was removed by vacuum filtration, and the solvent was evaporated and dried. The resulting powder was washed with 300 mL of distilled water. The resulting powder was again vacuum filtered and recrystallized from dichloromethane and hexane to obtain a yellow powder. Yield: 0.172 g, 34%. Elemental analysis(%):calcd.for C 76 H 96 EuNO8,C70.03,H7.42,N1.07;found,C69.21,H7.38,N1.05.

[0090] [Example 2] (Circularly polarized luminescent rare earth complex NEt4 + [Eu(+tfbc)4] - Synthesis of ((+)tfbc;(+)-3-(4-trifluoromethyl)benzoylcamphor) Under an argon gas atmosphere, NaH (1.89 g, 0.0788 mol) was washed with a small amount of hexane, followed by the addition of tetrahydrofuran (ultra-anhydrous, 40 mL) and (+)-camphor (3.02 g, 0.0198 mol) and stirring. The mixture was cooled to 0°C, and ethyl-4-(trifluoromethyl)benzoate (4.32 g, 0.0198 mol) was added and stirred for 10 minutes. After returning to room temperature, the mixture was heated to reflux at 70°C for 20 hours. The mixture was again cooled to 0°C, and hydrochloric acid (1 M) was added to adjust the pH to 1-2. The reaction solution was extracted with ethyl acetate and saturated brine, dehydrated over sodium sulfate, and the solvent was evaporated. The resulting residue was recrystallized from pentane to give yellow crystals (+tfbc). Yield: 1.47 g, 23%. 1 H-NMR (400MHz, CDCl3): δ / ppm=7.74-7.77(d,2H),7.66-7.70(d,2H),2.78-2.81(d,1H),2.1 3-2.21(m,1H),1.76-1.84(m,1H),1.50-1.64(m,3H),1.02(s,3H),0.94(s,3H),0.81(s,3H). 13 C-NMR (100MHz, CDCl3): δ / ppm=213.56,159.84,137.58,131.47-132.45(q),130.43,128.81, 128.22,125.41-125.45(d),122.51,57.91,50.15,48.46,30.62,27.10,20.43,18.79,8.92. 19 F-NMR (400MHz, CDCl3): δ / ppm=-62.79(s). IR(ATR):2960(st,arC-H)cm -1 ,1672(st,C=O),1610-1630(st,C=C)cm -1 ,1160(st,CF)cm -1 . ESI-Mass(m / z):[M+H] + calcd.for C 18 H 20 F3O2,325.14;found,325.14. Elemental analysis(%):calcd.for C 18 H 19 F3O2,C66.66,H5.90;found,C66.70,H5.91.

[0091] Next, +tfbc (0.331 g, 1.02 mmol) and NEt4Cl (0.103 g, 0.623 mmol) were each dissolved in 5 mL of ethanol. The two solutions were mixed and stirred for approximately 20 minutes. The pH of the mixture was adjusted to 8-9 using 0.5 M NaOH ethanol solution and further stirred for approximately 10 minutes. EuCl3·6H2O (0.137 g, 0.373 mmol) was dissolved in 5 mL of ethanol and added to the mixture. The pH was then adjusted to 8-9 and heated under reflux for 4 hours. The solvent was evaporated and the mixture was dried. The resulting powder was washed with 300 mL of distilled water. The mixture was filtered under reduced pressure and recrystallized from dichloromethane and hexane. The crystals were ground in a mortar and pestle and washed again with excess distilled water to obtain a yellow powder of NEt4. + [Eu(+tfbc)4] - Yield: 127.1 mg, yield: 32%. IR(ATR):2950(st,CH)cm -1 ,1588-1644(st,C=O,stC=C)cm -1 ,1167(st,CF)cm -1 . ESI-Mass (m / z): [M-NEt4] - calcd.for C 72 H 72 EuF 12 O8,1445.43,found,1445.43. Elemental analysis(%):calcd.for C 76 H 96 EuNO8,C60.99,H5.89,N0.89,F14.46;found,C59.97,H5.72,N0.83,F14.77.

[0092] [Comparative Example 1] (Circularly polarized luminescent rare earth complex NEt4 + [Eu(+hfc)4]- Synthesis of (+hfc:(+)-3-(heptafluorobutyryl)-D-camphor) (+)-3-(heptafluorobutyryl)-D-camphor (225 μL, 0.53 mmol), tetraethylammonium chloride (62.3 mg, 0.37 mmol), and europium(III) chloride hexahydrate (68.1 mg, 0.19 mmol) were each dissolved in 3 mL of ethanol. The three solutions were mixed, and the pH of the mixture was adjusted to 7 using NaOH ethanol. After stirring for 1 hour, the white precipitate was removed by filtration. The solvent from the resulting reaction solution was evaporated to yield a pale yellow powder. This powder was recrystallized from acetonitrile to yield pale yellow crystals. Yield: 106.8 mg, 34%. ESI-Mass(m / z)[M-NEt4] - calcd.for C 56 H 56 EuF 28 O8,1541.28,found,1541.24. Elemental analysis(%):calcd.for C 64 H 76 EuF 28 NO8,C46.00,H4.58,N0.84;found,C45.74,H4.46,N0.79.

[0093] Comparative Example 2 (Circularly polarized luminescent rare earth complex DAEA + [Eu(+hfc)4] - Synthesis of (DAEA + :2-(dimethylamino)-N,N,N-trimethylethane-1-aminium) (+)-3-(heptafluorobutyryl)-D-camphor (170 μL, 0.40 mmol) and Europium(III) Chloride Hexahydrate (55 mg, 0.15 mmol) were dissolved in ethanol (2 mL, 3 mL), respectively, and mixed. N,N,N',N'-Tetramethyl-ethylenediamine (100 μL) was slowly added dropwise, and the mixture was refluxed for 4 hours. After the reaction, the reaction mixture was left at room temperature and the solvent was slowly evaporated to obtain pale yellow crystals. Yield: 195 mg, 78%. ESI-Mass(m / z):[M-DAEA] - calcd.for C 56 H 56 EuF 28 O8,1541.28,found,1541.27. Elemental analysis(%):calcd.for C 62 H 73 EuF 28 N2O8,C44.91,H4.44,N1.69;found,C44.81,H4.43,N1.59.

[0094] [evaluation] The following evaluation of each circularly polarized luminescent rare earth complex was carried out with the powder packed in a quartz cell. (1) Emission spectrum measurement The emission spectra of each circularly polarized luminescent rare earth complex were measured, and the results are shown in Figure 1. The conditions for measuring the emission spectrum are as follows. Sample: Powder (packed in a quartz cell) Measurement equipment: Modular fluorescence spectrophotometer (FluoroLog-3, manufactured by HORIBA) Measurement conditions: Measurement wavelength range: 550-720 nm, Excitation wavelength: 360 nm, Measurement wavelength interval: 0.1 nm

[0095] From the results shown in Figure 1, the emission spectrum shows the characteristic 5 D0→ 7 F JThe emission bands corresponding to (J = 0-4) were observed. In particular, the very sharp emission (FWHM < 2 nm) and 5 D0→ 7 The strong luminescence intensity of F4 was confirmed.

[0096] (2) Luminescence decay behavior The luminescence decay behavior of the circularly polarized luminescent rare earth complexes of the examples and comparative examples was measured, and the results are shown in FIG. The conditions for measuring the luminescence decay behavior are as follows. Sample: Powder (packed in a quartz cell) Measurement equipment: Q-switched Nd:YAG laser (Spectra-Physics, INDI-50, fwhm = 5 ns, λ = 1064 nm), Hamamatsu Photonics R5108 photomultiplier (response time ≦ 1.1 ms), and Sony Tektronix TDS3052 Digital oscilloscope (500 MHz). Measurement conditions: Excitation wavelength: 355 nm, Detection wavelength: 610 nm

[0097] From the results shown in Figure 2, the luminescence decay behavior shows a decay on the microsecond scale, and the luminescence lifetime is observed as two different luminescence lifetimes, and the average value obtained by fitting is 425 μs. obs contains two components τ1 and τ2, the average of which is τ ave The proportion of each component and the emission lifetime are shown in Table 1. From the results shown in Table 1, it is clear that the long-life component is the main component, and it is presumed that this is due to the difference in the environment around the rare earth complex. In addition, the non-radiative rate constant k nr is the radiative rate constant k r It was estimated to be more than four times larger than NEt4 + [Eu(+hfc)4] - Compared to k r The value of does not change much, but k nr The values ​​of k are very different. nrThe difference in the value is presumed to be related to the LMCT level and the back energy transfer to the T1 level.

[0098] [Table 1]

[0099] (3) Luminous efficiency measurement The luminescence efficiency (Φ f-f ) was calculated from the emission spectrum and emission lifetime. The luminous efficiency (Φ f-f ) are shown in Table 2. Calculation method: The luminescence quantum yield Φ is calculated using the following formulas (α1), (α2), and (α3). f-f In the following formula (α1), A MD,0 =14.65s -1 , n is the relfactive index, I tot is the total area of ​​emission spectrum, I MD area of 5 D0→ 7 Represents F1. From the results shown in Table 2, it was confirmed that the circularly polarized luminescent rare earth complexes of the examples had luminous efficiencies equal to or higher than those of the circularly polarized luminescent rare earth complexes of the comparative examples, and were superior in luminous efficiency.

[0100]

number

[0101] [Table 2]

[0102] (4) Circular polarization characteristics KBr pellets were prepared from the circularly polarized luminescent rare earth complexes of Example 1 and Comparative Examples 1 and 2, and their circularly polarized luminescence (CPL) spectra were measured. The conditions for measuring the circularly polarized luminescence (CPL) spectrum are as follows. Measurement equipment: Circularly polarized luminescence measurement equipment (CPL-300, manufactured by JASCO Corporation) Excitation wavelength: 350 nm Sensitivity: 100mdeg. Scanning speed: 10 nm / min Measurement interval: 0.1nm

[0103] The circularly polarized luminescence (CPL) spectrum of the circularly polarized luminescent rare earth complex of Example 1 was measured and the results are shown in Figure 3. In Figure 3, the Eu(III) complex 5 D0→ 7 F1 and 5 D0→ 7 The CPL was observed accompanying the emission of F2, and its sign was reversed depending on the camphor ligand of the enantiomer. The g values ​​of CPL at 594 nm for the circularly polarized luminescent rare earth complexes of Example 1 are shown in Table 3.

[0104] [Table 3]

[0105] From the results shown in Table 3, NEt4 + [Eu(+bzc)4] - and NEt4 + [Eu(+tfbc)4] - is in the solid state, g CPL Very large g = +1.17 and +1.05 CPL It was shown to show value.

[0106] (5) Temperature dependence of circularly polarized luminescence The temperature dependence of the circularly polarized luminescence of the circularly polarized luminescence rare earth complex of Example 1 was evaluated. The CPL spectrum of the circularly polarized luminescent rare earth complex prepared in Example 1 was measured in an 8 mM methylene chloride solution at temperatures of 190 K, 200 K, 210 K, and 220 K. The temperature dependence of the circularly polarized luminescence of the circularly polarized luminescent rare earth complex of Example 1 is shown in Table 4 and FIG.

[0107] [Table 4]

[0108] From the results shown in Table 4, the circularly polarized luminescent rare earth complexes of the examples show that the circular polarization properties (g CPL It was confirmed that the value was higher.

Claims

1. A circularly polarized luminescent rare earth complex represented by the following general formula (1) or (2), or an enantiomer thereof: 【Chemical 1】 (In general formula (1), Ln ３＋ represents a trivalent rare earth ion. Each Z independently represents phosphine oxide (P=O) or phosphorus (P). Each Y independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, and for each phenyl group to which Y is bonded, at least one Y in the ortho position relative to Z is an alkoxy group, an ester group, or an acyloxy group, and hydrogen atoms in the hydrocarbon that may be contained in Y may each independently be substituted with a halogen atom. X represents a direct bond, or —O—, —S—, —NR— (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms), or a hydrocarbon group having 1 carbon atom. Each Q independently represents any one of a hydrogen atom, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, and a mercapto group, or may be bonded to each other to form a 6-membered aromatic hydrocarbon ring, and each hydrogen atom in the hydrocarbon that may be contained in Q may be independently substituted with a halogen atom. R １ represents an aromatic group having 6 to 22 carbon atoms or a heteroaromatic group having 4 to 22 carbon atoms, which may have a substituent. R ２ and R ３ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R ２ and R ３ Each hydrogen atom in the hydrocarbon that may be contained in may be independently substituted with a halogen atom. n1 represents a natural number from 0 to 6, n2 represents a natural number from 0 to 3, and n1+2×n2 is 0 to 6. m represents a natural number from 1 to 4. When n1 or n2 is 2 or more, the structures in the parentheses may be the same or different. A ＋ represents a monovalent cation, and m2 represents 0 or 1. 【Chemistry 2】 (In general formula (2), Ln ３＋ , R １ , R ２ , R ３ Y and Z are the same as those in the general formula (1), LL is a linker ligand coordinated to two or more of the rare earth ions, m is 1 to 3, and n1 is 0 to 4. Ln3+ may be the same or different. A ＋ represents a monovalent cation, and m3 represents 0 or 1.

2. 2. The circularly polarized luminescent rare earth complex according to claim 1, wherein the main chain of the general formula (2) contains one phosphoryl group represented by the following general formula (3) at an end of the main chain: 【Chemistry 3】 (In general formula (3), Ln ３＋ , R １ , R ２ , R ３ Y and Z are the same as those in the general formula (1), LL is a linker ligand coordinated to two or more of the rare earth ions, m is 1 to 3, and n1 is 0 to 4. ３＋ may be the same or different. ＋ represents a monovalent cation, and m3 represents 0 or 1.

3. 3. The circularly polarized luminescent rare earth complex according to claim 1, wherein the absolute configuration of the ligand around the rare earth ion is at least one of a right-handed helical Δ configuration and a left-handed helical Λ configuration.

4. A coating composition comprising the circularly polarized luminescent rare earth complex of claim 1.

5. A molded article or film comprising the circularly polarized luminescent rare earth complex according to claim 1.

6. An optically functional material comprising the circularly polarized luminescent rare earth complex according to claim 1 .

7. A three-dimensional display comprising the optically functional material according to claim 6.

8. A camphor derivative represented by the following general formula (4) and a monovalent cation A ＋ preparing a solution containing a salt consisting of adding a solution containing rare earth ions to the solution to react the camphor derivative with the rare earth ions to obtain a reaction product; and washing the reaction product with a solvent and then drying the same. R of the camphor derivative １ The method for producing a circularly polarized luminescent rare earth complex is to obtain at least one of a right-handed helical Δ form and a left-handed helical Λ form in which the absolute configuration of the ligand around the rare earth ion is either a right-handed helical Δ form or a left-handed helical Λ form by making the structure of the compound (I) a sterically bulky structure or a structure having a substituent, or by adding an optically active substance to the reaction solution. 【Chemistry 4】 (In general formula (4), R １ represents an aromatic or heteroaromatic group having 1 to 22 carbon atoms which may have a substituent. R ２ and R ３ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, a heteroaromatic group having 4 to 22 carbon atoms, an alkoxy group, an ester group, an acyloxy group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group; R ２ and R ３ Each hydrogen atom in the hydrocarbon may be independently substituted with a halogen atom.

9. 10. Use of the circularly polarized luminescent rare earth complex according to claim 1, wherein the circularly polarized luminescent rare earth complex is used at a temperature of -200°C or higher and 200°C or lower.

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