JP2000256251A - Rare-earth metal-carrying nano-size (host-guest) complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject inorganic rare-earth metal-carrying nano-size (host-guest) complex in which an inorganic host compound is allowed to support a rare earth metal ion or the like and the complex has excellent luminescence property, disperses homogeneously in a medium, for example, in a solvent without causing turbidity and is useful as an optically functional material. SOLUTION: An inorganic host compound (preferably zeolite, at least one selected from inorganic layer compounds and meso porous body) is allowed to support at least one selected from rare earth metal ion and rare earth metal complex to give the objective complex of nano-size particle with an average particle size of 1-200 nm. In a preferred embodiment, this complex has a Franck- Condon constant of 0-0.061 derived from the interatomic distance of the atoms that constitute the rare earth metal complex. The supported rare earth metal complex is preferably selected from those represented by formulas I and II [M is a rare earth atom; n1, n2 are each 2-4; Rf1-Rf3 are each a 1-22C aliphatic group or the like; X1-X3 are each a IVA atom or the like; n3-n5 are each 0, 1; and Y is C-Z group(Z is H, D (deuterium) or the like)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a nano-sized (host-guest) composite, a composition, and a molded article supporting rare earth metal ions and the like, and uses and production methods thereof.

[0002]

2. Description of the Related Art It is known that certain rare earth metal ions and rare earth metal complexes have luminous ability. For example, carboxylate-type rare earth metal complexes are known to be useful as light-emitting materials (for example, German Patent Application No. 3050703).

In recent years, methods for improving the luminous ability of these ions or complexes have been proposed. For example, Japanese Unexamined Patent Publication No.
No. 194941 proposes a light emitting material in which a rare earth metal ion and a ligand form a complex in a zeolite cavity. The content is to improve the heat resistance and / or chemical stability of the rare earth metal complex by inserting the rare earth metal complex into the zeolite cavity. Furthermore, the inclusion of zeolite states that the luminous body has a suspension behavour.

However, conventional zeolites containing a rare earth metal complex in their cavities become cloudy when formed into a composition with a medium such as a solvent or a polymer matrix, and when the composition is further irradiated with light. Since the zeolite has a particle diameter larger than the wavelength of light, light scattering is caused and transmission of light is hindered.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and mainly has a host-guest complex which has excellent light-emitting characteristics and does not become cloudy even when dispersed in a medium. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a nanosized (host-guest) in which a rare earth metal ion and / or a rare earth complex is supported as a guest on an inorganic host compound such as zeolite. ) Complex (hereinafter simply referred to as “host-guest complex” or “complex”
There is that. Has been found to be suitable for use as an optically functional material because it does not become cloudy and is uniformly dispersed in a medium such as a solvent.

Further, the present inventor has found that the emission characteristics of the rare earth metal ion or the rare earth metal complex are improved as compared with the case where the rare earth metal ion or the rare earth metal complex is used alone, and has found that the above-mentioned problem can be solved.

Further, the present inventors select, as the inorganic host compound, a compound in which the vibration of the inorganic skeleton (for example, in the case of zeolite, Si—O skeleton or Al—O skeleton) is low in the infrared spectrum. Thus, the inventors have found that the luminescence characteristics of the composite can be further improved.

That is, the present invention provides a (host-guest) composite having the following average particle diameter, a composition, a molded article,
It relates to a use and a manufacturing method. 1. A (host-guest) composite having a nano-size average particle diameter in which an inorganic host compound carries at least one selected from the group consisting of a rare earth metal ion and a rare earth metal complex. 2. A nano-sized (host-guest) composite in which an inorganic host compound carries a rare earth metal ion and has an average particle size of nano-size. 3. A nano-sized (host-guest) composite in which a rare earth metal complex is supported on an inorganic host compound and has an average particle size of nano-size. 4. At least one selected from the group consisting of a zeolite, an inorganic layered compound and a mesoporous material, wherein the inorganic host compound is
4. The nano-sized (host-guest) complex according to any of claims 1-3. 5. The nano-sized (host-guest) composite according to any one of claims 1 to 3, having an average particle diameter of 1 to 200 nm. 6. Nanosized (host-guest) according to any one of 1 to 3, wherein the Frank-Condon constant derived from the interatomic bond of the atoms constituting the rare earth metal complex is more than 0 and not more than 0.061. Complex. 7. The supported rare earth metal complex has the general formula (I):

[0010]

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[Wherein M represents a rare earth atom, and n1 represents 2
4 are shown. n2 represents 2, 3 or 4. Rf ¹ and Rf ² are the same or different and each are a C _1-22 aliphatic group,
X ¹ and X ² are the same or different and represent any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen; n3 and n4 each represent 0 or 1 is shown. Y is CZ (Z is hydrogen,
Deuterium, a halogen atom or a C _1-22 aliphatic group, an aromatic group or a cyano group), N, P, Sb or Bi. ]: And general formula (II)

[0012]

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Wherein M, n1 and n2 are as defined above. Rf ³ represents a C _1-22 aliphatic group, an aromatic group or a heterocyclic group, X ³ represents any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen; Indicates 0 or 1. ] The nano-sized (host-guest) complex according to any one of 1 to 3, which is at least one selected from the group consisting of complexes represented by the following formula: 8. The supported rare earth metal complex is represented by the general formula (II)
I):

[0014]

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Wherein M, n1 and n2 are as defined above. Rf ⁴ and Rf ⁵ are the same or different and represent a C _1-22 aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom. ] The nanosized (host-guest) complex according to any one of 1 to 3, which is a complex represented by the formula: 9. The supported rare earth metal complex has the general formula (IV):

[0016]

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Wherein M, Rf ⁴ , Rf ⁵ , n1 and n
2 is as defined above. ] The nano-sized (host-
Guest) complex. 10. The supported rare earth metal complex has a general formula (V):

[0018]

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Where M, Rf ⁴ , Rf ⁵ , n1 and n2
Is as defined above. Z ′ represents a deuterium, a C _1-22 aliphatic group containing no halogen or hydrogen atom, an aromatic group containing no hydrogen atom, and a cyano group. ]
4. The nanosized (host-guest) complex according to any one of 1 to 3, which is a complex represented by: 11. A composition in which the nano-sized (host-guest) complex according to any one of 1 to 9 is dispersed in a solvent. 12. A composition comprising the nanosized (host-guest) composite according to claim 1 dispersed in a polymer matrix. 13. A molded article comprising the composition according to item 11. 14. An optical functional material comprising the nano-sized (host-guest) composite according to any one of 1 to 9. 15. (a) stirring an inorganic host compound having an average particle diameter of nano-size and (b) at least one rare earth metal compound solution selected from the group consisting of rare earth metal oxides, rare earth metal alkosides, rare earth metal amides and rare earth metal salts; A method of producing a (host-guest) composite having a rare-earth metal ion and having an average particle size of nano-size, wherein the rare-earth metal ion is supported on an inorganic host compound. 16. General formula (VI):

[0020]

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[Wherein Rf ¹ , Rf ² , X ¹ , X ² , n3,
n4 and Y are as defined above. ]: And the general formula (VII):

[0022]

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Wherein Rf ³ , X ³ and n5 are as defined above. By vaporizing or sublimating at least one selected from the group consisting of compounds represented by the formula (1), a rare-earth metal complex in a nano-sized (host-guest) composite carrying a rare-earth metal ion, The method for producing a (host-guest) composite having a nano-size average particle diameter carrying a guest compound containing a rare earth metal complex, characterized by forming 17． General formula (VI):

[0024]

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[Wherein Rf ¹ , Rf ² , X ¹ , X ² , n3,
n4 and Y are as defined above. ]: And the general formula (VII):

[0026]

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Wherein Rf ³ , X ³ and n5 are as defined above. In the solution of the compound represented by the formula, by stirring the nano-sized (host-guest) complex having an average particle diameter supporting the rare-earth metal ion, the (host-guest) complex in the (host-guest) complex The average particle size supporting the guest compound containing the rare earth metal complex, which is characterized by forming a complex, is nano-sized.
A method for producing a (host-guest) complex.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Host-guest) according to the present invention
The complex refers to an inorganic host compound and at least one selected from the group consisting of a rare earth metal ion and a rare earth metal complex (hereinafter, may be simply referred to as a “guest compound”).
Is a (host-guest) complex carrying as a guest.

The average particle diameter of the primary particles of the (host-guest) composite of the present invention is not particularly limited as long as it is nano-sized, but is usually about 200 nm or less, preferably 1 nm or less.
The thickness is about 200 to 200 nm, more preferably about 1 to 150 nm, and particularly preferably about 1 to 100 nm. The average particle size of the (host-guest) complex of the present invention is determined by converting the (host-guest) complex into dimethyl sulfoxide (DMS).
O) and sonicated for 5 minutes to obtain 0.45 μl.
m is filtered using a filter of DLS (Dyn)
The particle size distribution was measured using Amic Light Scattering, and the number average value was obtained.

The (host-guest) composite of the present invention is prepared to have a predetermined average particle size regardless of whether the guest compound is supported on the inorganic host compound. For example, a method of synthesizing a host compound having a predetermined average particle diameter and supporting the guest compound on the host compound, or a method of preparing a host compound having a predetermined average particle diameter by crushing or the like, before or after loading, regardless of before or after loading In addition, a method of selecting particles having a predetermined average particle diameter by a method such as sieving, a combination thereof, and the like can be given.

When the (host-guest) complex of the present invention is used as a light-emitting material, the absorbed light energy is efficiently transferred to the guest compound, so that the vibration of the inorganic skeleton in the inorganic host compound (for example, zeolite) In the above, a compound whose Si—O skeleton or Al—O skeleton) does not have an absorption of 1500 cm ⁻¹ or more in an infrared absorption spectrum is recommended, and a compound that does not have an absorption of 1200 cm ⁻¹ or more is more preferable. If the frequency of the inorganic skeleton is too high, the absorbed energy is converted into heat energy, and the luminescence energy is easily lost.

The inorganic host compound used in the present invention has pores (mesopores), and atoms or molecules can be taken into the pores as guests. In the inorganic host compound used in the present invention, the pore diameter of the pores for taking in atoms or molecules is about 0.1 nm to 50 nm. Examples of such a compound include an inorganic layered compound, zeolite, mesoporous material, and the like.

Among the inorganic host compounds, examples of the inorganic layered compound include a layered silicate, hydrotalcite and the like.

The layered silicate is composed of an SiO ₄ tetrahedron as a basic structural unit, a Mg (OH) ₂ or Al (OH) ₃ octahedral layer connected to form a structural unit, and a sheet-shaped connected unit. It has a layered structure. Further, Na ⁺ , K ⁺ ,
Ca ^{2+ and the} like exist between layers as exchangeable cations. Layered silicates are classified into kaolinite, numectite, magatediite, kenyaite, kamemite, perovskite, montmorillonite, mica, etc. according to their composition, structural unit, cation amount, etc. Available to

Hydrotalcite is one of the naturally occurring layered minerals, and the natural one is generally Mg ₆ A
It can be represented by l ₂ (OH) ₁₆ (CO ₃ ). In the present invention, in addition to natural hydrotalcite, Mg ions and A
Synthetic hydrotalcite such as synthetic hydrotalcite in which l-ion is substituted with another transition metal ion and synthetic hydrotalcite in which CO ₃ anion is substituted with another anion can also be used.

Among the inorganic host compounds, zeolite is
It is a porous crystal in which a SiO ₄ tetrahedron and an AlO ₄ tetrahedron are bonded three-dimensionally.
L-type, Y-type, X-type, P-type, T-type, ZSM-5, silicalite, 1-hydroxysodalite (1-hydroxys
odalite), mesolite, leucolite, goethite, sodalite, mordenite, heulandite, bazite, nepheline and the like. Among these, A type, L type, Y type, X type,
ZSM-5, silicalite and 1-hydroxysodalite are preferred, and A-type, L-type, Y-type, X-type and ZSM-5 are particularly preferred. The pore size of the zeolite pores used in the present invention,
It is about 0.1 nm to 50 nm. The Si / Al ratio of the zeolite used in the present invention is not particularly limited.
It is about 00-1.

Among the inorganic host compounds, the mesoporous material is a porous material having pores (mesopore) having a pore size of about 1 nm to 50 nm. Specifically, FSM-1
6, mesoporous silica such as MCM-41.

The inorganic host compound may be any of a natural compound, a synthetic compound and a commercially available compound. The inorganic host compound used in the present invention can be used alone or in combination of two or more. The shape of the primary particles of the inorganic host compound used in the present invention does not matter.

When an inorganic host compound having a predetermined average particle diameter before supporting the host compound is used, it can be synthesized by a known method. For example, Zeolite, 1994, Vol. 14, 2
08 pages, Zeolite, 1994, Vol. 14, 1
10 pages, Zeolite, 1994, Volume 14, 5
57 pages, Zeolite, 1994, vol. 14, 6
Page 43, Chem. Mater, 1995, 7
Vol., Pp. 1734-1741, Zeolite, 19
For example, the synthesis method described in 1997, Vol. 18, p. 387 can be used.

Among the above inorganic host compounds, zeolite, hydrotalcite, numectite, and montmorillonite are recommended, and zeolite is more preferable.

The surface and / or interior of the inorganic host compound used in the present invention may be modified, if necessary. The modification reaction on the surface and / or inside of the inorganic host compound may be performed before or after supporting the guest compound, but preferably after the supporting.

By such a modification, for example, the dispersibility of the inorganic host compound in the solvent can be controlled. Specifically, by modifying the surface or the like of the inorganic host compound with a non-polar substituent, the dispersibility in a non-polar medium such as an organic solvent can be improved. Alternatively, by modifying the surface of the inorganic host compound or the like with a substituent having a charge, the individual inorganic host compound is electrostatically repelled,
Since it is difficult to associate, the dispersibility in a polar medium such as a polar solvent can be further improved.

Alternatively, the surface and / or the inside of the inorganic host compound can be modified with a photosensitizing functional group. Examples of such a functional group include a phenyl group, a tolyl group, a naphthyl group, a pyridyl group, a thienyl group, and derivatives thereof. Modification with a photosensitizing functional group can further improve the luminescent properties of the composite.

The surface of such an inorganic host compound and / or
Alternatively, a known method used for an inorganic host compound having a micro size or more can be used for the internal modification method. For example, layered silicate, hydrotalcite,
In the case of an inorganic host compound having a hydroxyl group on the surface and / or inside such as zeolite, a method described in Quarterly Chemistry Review Microporous Crystal, No. 21, 1994, edited by The Chemical Society of Japan, page 20, etc. Can be used. Specifically, Si of (SiO _{4) n} polymer end
It can be modified by reacting an OH group or an acidic OH group derived from (AlO ₄ ) ⁻ with an organic silane compound such as tetramethylsilane, an acid halide, or the like.

In the (host-guest) composite of the present invention, the rare earth metal ion supported on the inorganic host compound as a guest compound is not particularly limited as long as it is a rare earth metal ion. Examples of the rare earth metal ion include divalent to tetravalent ionic species of the rare earth metal element.
c, Y, La, Ce, Pr, Pr, Nd, Pm, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
Each ionic species of a rare earth metal such as u can be exemplified. Among these, divalent or trivalent ionic species are preferable, and Nd ³⁺ ,
Eu ³⁺ , Tb ³⁺ , Yb ³⁺ , Ce ³⁺ , Er ³⁺ , Tm ³⁺ , S
m ³⁺ is more preferred.

As a method for supporting the rare earth metal ion on the inorganic host compound, a known method for supporting an inorganic host compound having a size of micro size or more can be used. For example, an ion exchange method may be used. In the ion exchange method, the solution of the inorganic host compound and the rare earth metal compound may be stirred and further refluxed if necessary. The temperature for stirring is not particularly limited, but is usually about 10 to 200 ° C. The stirring time is not particularly limited, but is usually about 1 to 200 hours. Before loading the inorganic host compound,
It may be activated by heating at about 400 ° C. for about 1 to 30 hours. After stirring, excess rare earth metal ions may be removed by washing, dialysis, or the like. The (host-guest) complex supporting the rare earth metal ion can be separated by a method such as evaporation of the solvent and drying.

Rare earth metal used in ion exchange method
The compound is particularly restricted as long as it is a compound containing a rare earth metal element.
Not limited. For example, rare earth metal salts include M (Z) n
₁[M represents a rare earth atom. Z is chlorine ion, bromine ion
Ion, iodine ion, fluorine ion, 1/2 sulfate ion,
1/2 carbonate ion, nitrate ion, formate ion, acetate ion
Monocarboxylate ions such as oxalate ion
, Succinate, malonate, etc.
Acid ion), 1/3 (tricarboxylic acid such as citric acid)
ON) Indicates 1/3 (anions such as phosphate ion)
You. n₁Represents 2 or 3, preferably 3. ]etc
Is exemplified. M (OH) n is a rare earth metal hydroxide.
₁(M and n₁Is the same as above. ) Are exemplified; rare earth metals
As the alkoxide, M (OR¹) N₁(R¹Is al
Represents a kill group. M and n₁Is the same as above. ) Is an example
Rare earth metal amides include M (NR^aR^b) N
₁(R^aAnd R^bAre the same or different and represent hydrogen, alkyl,
Enyl, etc. M and n₁Is the same as above. ) Is an example
As a rare earth metal oxide, a trivalent rare earth atom
M including _TwoO_Three(M is the same as described above.)
O, M_FourO₇Other forms of oxide may be used. This
These compounds depend on the purpose, application, solvent used, etc.
It can be selected as appropriate. One or more of these compounds
Alternatively, two or more kinds can be used.

The solvent used in the ion exchange is not particularly limited. Examples thereof include water, DMSO, DMF (dimethylformamide), formamide, acetamide, HM
PA (hexamethylphosphoric triamide), nitromethane,
Examples thereof include acetonitrile, methanol, and a mixed solvent thereof.

The amount of the solvent in the ion exchange is not particularly limited, but is usually 1 to 1 part by weight of the inorganic host compound.
It is about 500 parts by weight, preferably about 10 to 200 parts by weight.

The ratio between the rare earth compound and the inorganic host compound at the time of ion exchange is not particularly limited, but can be appropriately set depending on the kind of the inorganic host compound or the rare earth compound to be used. For 1 part by weight of the inorganic host compound,
Usually about 0.01 to 50 parts by weight, preferably 0.1 to 10 parts by weight.
It is about.

After ion exchange, excess rare earth metal ions can be separated from the (host-guest) complex by a method such as washing and dialysis. The obtained (host-guest) complex can be separated by a method such as evaporation of the solvent and drying.

The rare earth metal ion-supported (host-guest) complex thus obtained can be used as a raw material for a guest compound-supported (host-guest) complex containing a rare earth metal complex.

The amount of the rare earth metal ion carried on the inorganic host compound can be appropriately set depending on the purpose and application. The loading amount of the rare earth metal ion is usually 0.01 to 1
It is about 00%, preferably about 0.1-33%. The amount of the rare earth metal ion carried is the weight ratio of the rare earth metal ion to the inorganic host compound.

On the other hand, when a synthetic inorganic host compound is used, a rare-earth metal compound is added at the synthesis stage to produce a (host-guest) composite, and then, if necessary, the average particle diameter is reduced to nano-size. It is also possible to prepare.
In that case, when mixing the inorganic salts as the raw material of the inorganic host compound, a rare earth metal compound or the like may be added at the same time, and the inorganic host compound may be prepared using a known method. However, for the purpose of supporting rare earth metal ions in the pores of the inorganic host compound,
That is, in order to increase the emission intensity and the like, a method of supporting a guest compound on the prepared inorganic host compound is preferable.

Hereinafter, a guest compound-supported (host-guest) complex containing a rare earth metal complex will be described.

The rare earth metal complex to be supported on the inorganic host compound may be appropriately selected according to the purpose and use. For example, when used as an optical functional material, the central metal is N
d ³⁺ , Eu ³⁺ , Tb ³⁺ , Yb ³⁺ , Ce ³⁺ , Tm ³⁺ , Er
Complexes of ³⁺ and Sm ³⁺ are preferred.

Examples of the complex to be supported include: 1) a rare earth complex of an organic carboxylic acid in which a carboxylic acid group and an organic group having at least three conjugate groups capable of being conjugated thereto are combined; A compound having a heteroatom in the molecule, in which two heteroatoms and a rare earth metal atom are combined to form a 5- or 6-membered ring, 3) a general formula (I) or (II) ), And 4) a complex containing a rare earth metal ion.

1) A carboxylic acid group and a carboxylic acid group
Not bonded to an organic group having at least three functional groups
Rare earth complexes of organic carboxylic acids such as aliphatic carboxylic acids such as 2,4,6-octatrienoic acid and 2,4,6,8-decatetraenoic acid; Benzoic acid, o-toluic acid, m-toluic acid, m-phthalic acid, terephthalic acid,
Aromatic carboxylic acids such as p-chlorobenzoic acid, p-methoxybenzoic acid, cuminic acid, trimellitic acid, etc., polycyclic carboxylic acids such as α-naphthoic acid, β-naphthoic acid, anthracene carboxylic acid, anthraquinone carboxylic acid, and thiophene Heterocyclic carboxylic acids such as carboxylic acid and nicotinic acid; α, β-unsaturated carboxylic acids such as cinnamic acid and p-methylcinnamic acid; and substituted products thereof. 2) a compound having at least two heteroatoms in the molecule
Two heteroatoms and a rare earth metal atom
Rare earth complex formed together with a 5- or 6-membered ring
The ligand of the body the complex, for example, 8-quinolinol, 1,10-phenanthroline, bipyridine, 7-hydroxyindole, 2-hydroxy-thiophene, 2-
Examples thereof include hydroxypyridine, benzoquinolinol, benzoxazole, benzothiazole, oxadiazole, thiadiazole, phenylbenzimidazole, bathophenanthroline, and phthalocyanine.

These compounds are described in “Organic EL Devices and Their Forefront of Industrialization, Supervised by Seizo Miyata, NTS Publishing, 39-
Page 43 ".

The rare earth complex represented by the general formula (I) described in the following 3) is also a compound having at least two hetero atoms in the molecule, and includes two hetero atoms and a rare earth metal atom. And 5 members ring or 6
Although it can be classified into a rare earth complex having a member ring, it is described separately here. 3) Rare earth metal complex represented by general formula (I) or (II) Specifically, general formula (I)

[0061]

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[Wherein M represents a rare earth metal atom and n1
Represents 2 or 3. n2 represents 2, 3 or 4. R
f ¹ and Rf ² are the same or different and each represents a C _1-22 aliphatic group, an aromatic group or a heterocyclic group, and X ¹ and X ²
Is the same or different as group VA and VA excluding nitrogen
A group atom or a VIA group atom excluding oxygen, and n
3 and n4 represent 0 or 1. Y represents CZ (Z represents a hydrogen, deuterium, halogen atom or C _1-22 aliphatic group, aromatic group, cyano group), N, P, Sb or Bi. Or a general formula (II)

[0063]

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Wherein M, n1 and n2 are as defined above. Rf ³ represents a C _1-22 aliphatic group, an aromatic group or a heterocyclic group, X ³ represents any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen; Indicates 0 or 1. ] Is a rare earth metal complex represented by

The ligand of such a complex includes sulfonamides, sulfonimides, β-diketones, sulfonic acids, phosphoric acids and the like. 4) Complex containing rare earth metal ion Examples of such a complex include a metal cluster containing a rare earth metal ion such as phosphotungstic acid and tungstic acid.

Among these complexes 1) to 4), when used as a light emitting material, the Frank-Condon constant derived from the interatomic bond of the atoms constituting the rare earth metal complex exceeds 0 to 0.061 or less. Are preferred.

When the Frank-Condon constant exceeds 0 to 0.0
Examples of the rare earth metal complex having 61 or less include complexes represented by the following general formulas (III) to (V).

Here, the Frank-Condon constant is defined as (“luminescence in Nd (III) solution”, Shozo Yanagida, et al.
Photochemistry, Vol. 26, pp. 22-29, 1997), which is used for light emission without losing the excited state of rare earth ions formed by light irradiation as heat energy (vibration excitation energy transfer). It is an index, and the smaller the value, the more the received energy can be used for light emission without losing it as heat energy.

The Frank-Condon constant (F) of the rare-earth metal complex can be calculated using the equation (1).

[0070]

(Equation 1)

Here, γ is represented by equation (2), but is calculated assuming γ = 1 for convenience of calculation.

[0072]

(Equation 2)

In the formula (1), ν represents a vibration quantum that resonates with the energy gap of the trivalent rare earth metal ion.

FIG. 1 shows the relationship between the vibration frequency, vibration overtone, and vibration quantum resonating with the energy gap of Nd ³⁺ at the binding site of the molecule in the case of the Nd complex.

A specific example of a rare-earth metal (for example, Nd) complex which is composed of Frank
The following are examples of the condon constant. Kind of interatomic bond: Frank-Condon constant OH: 0.18 CH: 0.18 CD: 0.061 CF: 0.0031 OD: 0.061 CC: 0 .042 C—O: 0.042 S—O: 0.0031 Nd—O: less than 0.001 That is, in the molecule of the ligand forming the rare earth metal complex,
Those containing many -D bonds and CF bonds tend to have a small Frank-Condon constant, and those containing many CH bonds and OH bonds tend to have a large Frank-Condon constant.

Accordingly, from the viewpoint of the Frank-Condon constant, a ligand forming a rare earth metal complex contains a C—F bond,
Rare earth metal complexes represented by the following general formulas (III) to (V) containing a CD bond are preferred.

[0077]

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Where M, Rf ⁴ , Rf ⁵ , n1 and n
2 is as defined above. ].

[0079]

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Wherein M, Rf ⁴ , Rf ⁵ , n1 and n
2 is as defined above. ]

[0081]

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Wherein M, Rf ⁴ , Rf ⁵ , n1, n2 and Z ′ are as defined above. ].

In these rare earth metal complexes, the C ₁ -C ₂₂ aliphatic group containing no hydrogen atom includes: * a perfluoroalkyl group (C _n F _{2n + 1} ; n = 1 to 2)
2), a perchloroalkyl group (C _n Cl _{2n + 1} ; n = 1 to
22) a linear or branched perhalogenated alkyl group such as trichloromethyl, trifluoromethyl, pentachloroethyl, pentafluoroethyl,
Heptachloropropyl, heptafluoropropyl, heptachloroisopropyl, heptafluoroisopropyl,
Nonachlorobutyl, nonafluorobutyl, nonachloroisobutyl, nonafluoroisobutyl, undecachloropentyl, undecafluoropentyl, undecachloroisopentyl, undecafluoroisopentyl, tridecachlorohexyl, tridecafluorohexyl, trideca Chloroisohexyl, tridecafluoroisohexyl,
Pentadecachloroheptyl, pentadecafluoroheptyl, pentadecachloroisoheptyl, pentadecafluoroisoheptyl, heptadecachlorooctyl, heptadecafluorooctyl, heptadecachloroisooctyl,
Heptadecafluoroisooctyl, nonadecachlorononyl, nonadecafluorononyl, nonadecachloroisononyl, nonadecafluoroisononyl, henicosachlorodecyl, henicosafluorodecyl, henicosachloroisodecyl, henicosa Fluoroisodecyl, tricosachloroundecyl, tricosafluoroundecyl, tricosachloroisoundecyl, tricosafluoroisoundecyl, pentacosachlorododecyl, pentacosafluorododecyl, pentacosachloroisododecyl, pentacosafluoroisododecyl , Heptacosachlorotridecyl,
Heptacosafluorotridecyl, heptacosachloroisotridecyl, heptacosafluoroisotridecyl, etc .; * perfluoroalkenyl group (perfluorovinyl group, perfluoroallyl group, perfluorobutenyl group, etc.), perchloroalkenyl group, etc. A C ₂ -C ₂₂ perhalogenated alkenyl group having a straight or branched chain, preferably trifluoroethynyl, trichloroethynyl, pentafluoropropenyl, pentachloropropenyl, heptafluorobutenyl, heptachlorobutenyl and the like; fluoroalkynyl groups, C ₂ -C ₂₂ perhalogenated alkynyl groups having a linear or branched, such as perchlorethylene alkynyl group; * perfluorocycloalkyl group _{(C n F 2n-1;} n =
3 to 22, preferably 3 to 8, more preferably 3 to
6), a perchlorocycloalkyl group (C _n Cl _2n-1 ; n)
= 3 to 22, preferably 3 to 8, more preferably 3 to
6) C ₃ ~C ₂₂ perhalogenated cycloalkyl groups such as, preferably, pentachlorophenol cyclopropyl, pentafluorocyclopropyl, hepta-chloro cyclobutyl,
Heptafluorocyclobutyl, nonachlorocyclopentyl, nonafluorocyclopentyl, undecachlorocyclohexyl, undecafluorocyclohexyl, tridecachlorocycloheptyl, tridecafluorocycloheptyl, pentadecachlorocyclooctyl, pentadecafluorocyclooctyl, etc .; C _3- such as fluorocycloalkenyl group (perfluorocyclopentenyl group, perfluorocyclohexenyl group, etc.) and perchlorocycloalkenyl group
C ₂₂ , preferably C _{3 to} C ₈ , more preferably C _{3 to} C ₆ perhalogenated cycloalkenyl groups; and * perhalogenated aralkyl groups such as perfluorobenzyl group and perfluorophenethyl group.

Examples of the aromatic group of the “aromatic group containing no hydrogen atom” include phenyl, naphthyl, anthranyl, phenanthryl, pyrenyl, biphenyl and the like; examples of the heterocyclic group of the “heterocyclic group containing no hydrogen atom” include: Pyridyl,
Thienyl, pyrrolyl, pyrimidinyl, quinolyl, isoquinolyl, benzimidazolyl, benzopyranyl, indolyl, benzofuranyl, imidazolyl, pyrazolyl, biphenyl, etc. a halogen atom such as a bromine atom, a nitro group, a cyano group, a nitroso group, C ₁ -C ₄ perhalogenated alkyl group (trifluoromethyl etc.), perhalogenated alkoxy group C ₁ -C ₄ (trifluoromethoxy etc. ), A C ₂ -C ₅ perhalogenated alkylcarbonyl group (such as trifluoroacetyl);
C ₂ -C ₅ perhalogenated alkoxycarbonyl group (trifluoromethoxyacetyl etc.), C ₁ -C ₄ perhalogenated alkylenedioxy group (difluoromethylenedioxy etc.), C ₂ -C ₅ perhalogenation It is substituted with a substituent not containing a hydrogen atom such as an alkenyl group (eg, perhalogenated vinyl), a perhalogenated phenoxy group, and a C _{2 to} C ₂₂ perhalogenated alkylcarbonyloxy.
Specific examples of the aromatic group containing no hydrogen atom include a perfluorophenyl group, a perchlorophenyl group, a perfluoronaphthyl group, a perchloronaphthyl group, a perfluoroanthranyl group, a perchloroanthranyl group, a perfluorophenanthryl group, A perchlorophenanthryl group is exemplified, and a heterocyclic group containing no hydrogen atom is, for example, a perhalogenated 2-pyridyl group.

One or more of the halogen atoms bonded to the aromatic or hetero ring of the perhalogenated aromatic group, perhalogenated heterocyclic group or perhalogenated aralkyl group may be selected from cyano, nitro, nitroso, C ₁ -C It may be substituted with a substituent not containing a hydrogen atom, such as C ₄ perhalogenated alkoxy, C ₂ -C ₅ perhalogenated alkoxycarbonyl, and C ₂ -C ₂₂ perhalogenated alkylcarbonyloxy.

Also, a C ₁ -C ₂₂ perhalogenated alkyl group, a C ₂ -C ₂₂ perhalogenated alkenyl group, a C ₂ -C ₂₂
One or more —O—, —COO—, and —CO— may be interposed between C—C single bonds at any position of the perhalogenated alkynyl group to form an ether, ester or ketone structure.

X ¹ and X ² represent C, Si, Ge, Sn,
It represents any one of a group IVA atom such as Pb, a group VA atom excluding nitrogen such as P, Sb and Bi, and a group VIA atom excluding oxygen such as S, Se, Te and Po, and is preferably C, S or
P or Se, more preferably C or S.

X ³ is an I such as Si, Ge, Sn, Pb, etc.
It represents any one of a group VA atom, a group VA atom excluding nitrogen such as P, Sb and Bi, and a group VIA atom excluding oxygen such as S, Se, Te and Po, and preferably S.

Y is CZ ′ (Z ′ is the same as above), N,
P, Sb or Bi, preferably CZ '(Z' is as defined above), N or P.

Z 'is a C ₁ -C ₂₂ aliphatic group containing no deuterium, halogen atom or hydrogen atom, preferably deuterium or a linear or branched C ₁ -C ₂₂ perhalogenated alkyl group. Is shown.

Z ″ ′ represents H or Z ′.

N1 represents 2 or 3, preferably 3.

N2 represents 2 to 4, preferably 2 or 3, especially 3.

N3, n4 and n5 are 0 or 1. In particular, when X ¹ , X ² or X ³ is S, n3, n4 or n5
Is preferably 1. When X ¹ or X ² is C, n3 or n4 is 0.

Further, as another viewpoint for increasing the light emitting property,
Is a side chain functional group (Rf¹, Rf^Two, Rf ^Three, Rf^Four, R
f^Five) With a ligand having a functional group that sensitizes light
Rare earth metal complexes are also recommended. As such a functional group
Is, for example, an aromatic group, a heterocyclic aromatic group, or the like.
You.

In particular, when the phosphorescence spectrum of the aromatic group is an aromatic group that overlaps with the absorption spectrum of the rare earth metal ion as the central metal, the light emission characteristics can be significantly improved. Examples of such an aromatic group include a phenyl group, a naphthyl group, a pyridyl group, an imidazoyl group, a phenanthrene group, a thienyl group and the like.

The rare earth metal ion in the inorganic host compound can coordinate two, three, or four molecules of a ligand, while a complex having four molecules coordinated is a small component, and is composed of two or three molecules. A major component is a complex in which a ligand of a molecule, in particular, a ligand of three molecules is coordinated.

In the guest compound-supported (host-guest) complex containing the rare earth metal complex, not all the rare earth metals need to be complexed. The ratio between the rare-earth metal complex and the ion in the guest compound-supported (host-guest) complex including the metal complex can be appropriately set depending on the use or the like. The ratio of the rare earth metal complex in the composite is 100% based on the total amount of the rare earth metal ion and the complex.
% Or less, preferably 30% or less, more preferably 0.1% or less.
About 10%.

The ligand of the complex supported on the (host-guest) complex is a known compound or can be easily synthesized from a known compound. For example, Journa
lof Chemical and Engineeri
ng Data, Vol. 16, No. 3, (1971),
The Journal of Organic Chem
The compound can be synthesized according to a method described in a literature such as “Istry, Vol. 35, No. 4, (1970)”. Alternatively, a commercially available product may be used.

The method for supporting the rare earth metal complex on the inorganic host compound is not particularly limited, and a known method for supporting an inorganic host compound having a micro size or more can be used. For example, there is a ship-in-bottle method. The ship-in-bottle method means that a complex supporting a rare earth metal ion is (1) vaporized with a corresponding ligand and brought into contact with the complex, or (2) a rare earth metal ion is dissolved in a corresponding ligand solution. By stirring the supported complex,
This is a method of transporting a ligand into a complex and forming a complex in the complex.

Examples of the corresponding ligand include the following compounds. General formula (VI):

[0102]

Embedded image

[Wherein Rf ¹ , Rf ² , X ¹ , X ² , n3,
n4 and Y are as defined above. ]: And the general formula (VII):

[0104]

Embedded image

Wherein Rf ³ , X ³ and n5 are as defined above. A method for preparing a (host-guest) complex supporting a guest compound containing a rare-earth metal complex using the ship-in-bottle method will be specifically described below.

As the (host-guest) complex carrying a rare earth metal ion used in the ship-in-bottle method, the rare earth metal ion carrying (host-guest) complex obtained by the above-mentioned method can be used. . It does not matter whether the rare earth metal ion-supported (host-guest) composite used has a predetermined average particle size. Before transporting the ligand to the rare-earth metal ion-carrying (host-guest) complex, a pretreatment for removing adsorbed water and the like in the complex may be performed. Specifically, normal pressure,
Preferably, heating is performed for about 1 to 20 hours under reduced pressure or vacuum. The heating temperature can be appropriately set depending on the pressure and the like, and is usually about 100 to 500 ° C. (1) When contacting with a vaporized ligand The corresponding ligand is vaporized or sublimated and transported into the rare-earth metal ion-supported (host-guest) complex. The temperature and pressure at which the ligand is vaporized can be appropriately set depending on the type of the ligand to be used.
The temperature for vaporization is usually about 10 to 250C, preferably about 20 to 200C. The pressure at the time of vaporization may be normal pressure, but is preferably performed under reduced pressure or vacuum. The time for bringing the ion-supported (host-guest) complex into contact with the vaporized ligand is not particularly limited,
Usually, it is about 0.5 to 50 hours, preferably about 1 to 40 hours. (2) In the case of stirring in a ligand solution The rare-earth metal ion-supported (host-guest) complex is stirred in the corresponding ligand solution, and refluxed if necessary to form a complex. The stirring time is not particularly limited, but is usually about 1 to 100 hours. The stirring temperature is not particularly limited, but is usually about 10 to 200 ° C. The solvent is
There is no particular limitation, and it can be appropriately selected depending on the kind of the ligand to be used and the like. For example, a protic solvent and an aprotic solvent are mentioned. As a protic solvent,
Water, alcoholic solvents such as methanol, ethanol and the like, and aprotic solvents include ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, halogen solvents such as chloroform and methylene chloride, DMSO , DMF and the like. The amount of the solvent used is, for example, about 1 to 500 parts by weight, preferably about 10 to 200 parts by weight, per 1 part by weight of the (host-guest) complex.

The amount of the ligand used in the methods (1) vaporization and (2) stirring can be appropriately set depending on the kind of the ion-supporting (host-guest) complex to be used. The amount of the ligand is usually about 1 to 50 equivalents, preferably 1.05 equivalents, per equivalent of the corresponding metal ion.
About 5 equivalents. The rare earth metal complex supported on the inorganic host compound can be prepared using one or more kinds of ligands.

After complex formation in the (host-guest) complex, the excess ligand can be removed by a known separation method such as extraction. Next, the (host-guest) complex can be separated by a method such as distilling off the solvent.

Since the size of the rare earth metal complex is usually larger than the size of the pores of the inorganic host compound, once formed in the inorganic host compound, the rare earth metal complex exits from the pores of the (host-guest) complex. Can not do.

The nano-sized (host-guest) composite of the present invention is usually in the form of a powder, but the powder can be used as a molded film. As a method of forming a molded film, for example, a known method such as a method of compressing a powder or a casting method can be used.

When the nano-sized (host-guest) complex of the present invention is used as a light emitting material, it is preferable to remove coordination water of the guest compound, adsorbed water of the (host-guest) complex and the like. Examples of the removal method include normal-pressure drying and vacuum drying. At the time of drying, if necessary, heating (for example, about 50 ° C. to 250 ° C.) may be performed under the condition that the guest compound is not decomposed.
Alternatively, by coordinating water or adsorbed water with a deuterium solvent, coordinating water of the guest compound, adsorbed water of the (host-guest) complex, and the like can be removed. For example, Me
OD, deuterium solvent and the like D ₂ O - After the (host-guest) vacuum by freezing and complex, and left for about 24 hours at room temperature and then and a method of distilling off the deuterated solvent Can be Substitution with the deuterium solvent is performed simultaneously (host-
Guest) -OH group on the surface and / or inside of the composite is replaced with -OD
Since it is converted into a group, it is more effective to improve the light emission characteristics. These methods can be performed alone or in combination.

In particular, a complex from which the adsorbed water, coordinating water, and the like contained in the pores of the (host-guest) complex have been removed by the above method or the like tends to have a high luminescence intensity. preferable.

Among the (host-guest) complexes of the present invention, from the viewpoint of light emission, a (host-guest) complex supporting a guest compound containing a rare earth metal complex is preferable.

The nano-sized (host-guest) composite of the present invention may be added with a compound for sensitizing light (that is, a photosensitizer) for the purpose of further increasing the luminescence, if necessary. good. Examples of such a compound include compounds having an aromatic group, a heterocyclic aromatic group, and the like. Specifically, for example, benzene, toluene, pyridine, bipyridine, naphthalene, anthracene, triphenylene, quinoline, phenanthrene, biphenyl, p-
Terphenyl, triphenylphosphine, triphenylphosphine oxide, and various organic dyes, for example, Polymer Functional Materials Series 6, Optical Functional Materials, edited by The Society of Polymer Science, 345 pages of Kyoritsu Shuppan (1991), or Fine Chemicals, published by CMC, 28 volumes, 3
No., pp. 5-18, (1999), such as monomethine dyes, trimethine dyes, cyanine dyes, pyrylium dyes, polymethine dyes,
Oxazine dye, xanthene dye, coumarin dye, terphenylene dye, etc.).

The method of adding the photosensitizer is not particularly limited. For example, a method of mixing the photosensitizer with a composite or an inorganic host compound, or a method of vaporizing or sublimating the photosensitizer to form the composite or A method of supporting on an inorganic host compound,
A method of stirring the complex or the inorganic host compound in the solution of the photosensitizer, refluxing as necessary, and supporting the complex or the inorganic host compound on the complex or the inorganic host compound is exemplified.

The step of adding the photosensitizer is not particularly limited. For example, the step after the supporting of the guest compound or the step after removing the adsorbed water and / or the coordinating water contained in the pores and the like can be mentioned. Is exemplified. Among these, adsorbed water and / or
Alternatively, a step after removing coordination water by heat treatment or the like is recommended.

The (host-guest) complex of the present invention may further contain a polar solvent, if necessary, for the purpose of increasing luminescence. The amount of polar solvent added was
The polar solvent is usually used in an amount of about 0 to 2,000 parts by weight, preferably about 0 to 1,000 parts by weight, based on 00 parts by weight.

As the polar solvent, for example, DMSO, D
Examples include aprotic polar solvents having a higher dielectric constant than water, such as MF, formamide, acetamide, HMPA, nitromethane, acetone, THF, and methanol, and deuterium-substituted products thereof. Among these polar solvents, D
Preferably deuterium substituted polar solvents, such as MSO and DMSO-d _6, polar solvents that are deuterated is more preferable.

The method for adding the polar solvent is not particularly limited, and examples thereof include a method of mixing an inorganic host compound or a complex with a predetermined amount of a polar solvent.

The step of adding the polar solvent is not particularly limited. For example, a step in which the guest compound is supported on the inorganic host compound, and after the supporting, the adsorbed water and / or coordinated water contained in the pores is subjected to heat treatment or the like. The stage after the removal is exemplified, and the stage after the removal of the adsorbed water and / or coordination water by heat treatment or the like is more preferable.

The nanosize (host-guest) complex of the present invention may contain various surfactants, if necessary, in addition to the photosensitizer and the polar solvent. Examples of such a surfactant include an ammonium salt, a quaternary ammonium salt, a pyridine salt, and a phosphoric acid surfactant. Perhaps because the surfactant is adsorbed on the surface of the (host-guest) complex by adding the surfactant, the (host-guest) complex is easily solvated and the dispersion state in the medium is stabilized. I do.

The method for adding the surfactant is not particularly limited. For example, a method in which the surfactant is mixed with a complex or an inorganic host compound, or a method in which the surfactant is vaporized or sublimated to give a complex or an inorganic host compound. How to carry,
A method in which a complex or an inorganic host compound is stirred in a solution of a surfactant, refluxed as necessary, and supported on the complex or the inorganic host compound may be mentioned.

Further, to the (host-guest) complex of the present invention, if necessary, a ligand having a complex forming ability can be further added. Such ligands include:
For example, the ligands used in the present invention, specifically, β-diketones such as hexafluoroacetylacetone, and sulfonimides such as perfluoroalkanesulfonimide are exemplified. These ligands may or may not be the same as the ligands of the rare earth metal complex in the composite. By adding these ligands, the (host-guest) complex is easily solvated, and the dispersion state in the medium is stabilized. It is considered that one of the causes is that these ligands form a complex with Al-OH, Si-OH, or the like existing on the surface of the inorganic host compound.

The method of adding a ligand having a complex-forming ability is not particularly limited. For example, a method of mixing a ligand having a complex-forming ability with a complex or an inorganic host compound, or a method having a complex-forming ability A method in which a ligand is vaporized or sublimated and supported on a complex or an inorganic host compound, and a complex or an inorganic host compound is stirred in a solution of a ligand having a complex-forming ability, and refluxed if necessary, thereby forming a complex. Alternatively, a method of supporting the compound on an inorganic host compound may be used. Alternatively, after supporting the rare earth metal in the composite, the ligand may be used as it is without removing the excess ligand.

The nano-sized (host-guest) complex of the present invention does not become cloudy when dispersed in a medium such as a solvent or a polymer matrix, so that it can be suitably used as an optical functional material.

For example, it is useful for applications such as light-emitting materials, EL devices, optical fibers, inks, lenses, and immunoassays.
It can be used for remote control, copy equipment, laser printer, large display, medical laser, laser processing measurement, optical equipment such as printing related, specifically, laser element, light emitting diode, liquid crystal, optical fiber, photo detector,
It can be applied to solar cells and optical materials for immunoassay detection.

In particular, as a luminescent ink material, the (host-guest) composite of the present invention is suitable because it has a small average particle diameter and is easily dispersed in a medium.

The compound represented by the general formula (II) or the general formula
The (host-guest) complex containing the rare earth metal complex represented by (IV) can be used as a Lewis acid catalyst in addition to the photofunctional material.

The (host-guest) complex of the present invention can be dispersed in a medium such as a solvent or a polymer matrix to form a composition. The medium in which the (host-guest) complex is dispersed is not particularly limited as long as it is a medium usually used in the art.

The (host-guest) complex in the medium may be aggregated to some extent. The degree of agglomeration varies depending on the use, the type of medium, and the like, but may be such that transparency in the medium can be visually confirmed. The average particle size of the aggregate is usually about 3000 nm or less, preferably about 1000 to 100 nm, more preferably about 500 nm.
About 100 nm. The average particle size of the aggregate is determined by the same measurement method as the average particle size of the (host-guest) complex.

The ratio between the nano-sized (host-guest) complex of the present invention and the medium can be appropriately set depending on the use, the type of the medium to be used, and the like. In 100 parts by weight of the composition of the present invention, the nano-sized (host-guest) complex is usually about 0.001 to 20 parts by weight, preferably 0.1 to 20 parts by weight.
It contains about 1 to 10 parts by weight. The medium is usually 99.999-
About 80 parts by weight, preferably about 99.9 to 90 parts by weight.

Nano-size (host-guest) of the present invention
As a method of dispersing the complex in the medium, a known method for dispersing another compound in the medium can be used.

Hereinafter, a composition using a solvent or a polymer matrix as a medium will be described in detail.

As a solvent for dispersing the nano-sized (host-guest) complex of the present invention, for example, water; DMS
O, DMF, formamide, acetamide, HMPA,
Polar solvents such as nitromethane, acetonitrile, methanol and ethanol, benzene, toluene, xylene, n
Non-polar solvents such as -hexane and cyclohexane, substituted deuterates thereof, and mixed solvents thereof;
These solvents can be appropriately selected depending on the purpose, use, and the like. For example, when used as a light-emitting material, a solvent substituted with deuterium is preferable because the light-emitting characteristics are improved.

The method of dispersing the nano-sized (host-guest) complex of the present invention in a solvent is not particularly limited. For example, the dispersion can be performed by adding the (host-guest) complex to the solvent and stirring. A suspension method and the like can be mentioned. At this time, if necessary, the suspension may be dispersed using an ultrasonic stirring device or the like. The dispersion may be filtered to remove the complex (host-guest) that could not be dispersed. Alternatively, after standing for a long time, the supernatant may be used.

The composition of the present invention has a nano-size (host-
Guest) The composite can be produced by dispersing or suspending the composite in a polymer matrix. Further, a polar solvent such as DMSO may be further added as needed.

The polymer matrix for dispersing the nano-sized (host-guest) complex of the present invention is not particularly limited as long as it is commonly used in the art. Particularly, those which can be visually confirmed to be transparent are preferable.

As such a polymer matrix, for example, polymethacrylate (PMA), polymethyl methacrylate (PMMA), poly (hexafluoroisopropyl methacrylate) (P-iFPMA), poly (hexafluoro-n-propyl methacrylate) ( P-n
FPMA) and other fluorinated polyacrylates such as polyacrylate and polyfluoroisopropyl acrylate, polyolefins such as polystyrene, polyethylene, polypropylene and polybutene, fluorinated polyolefins, polyvinyl alcohol, polyvinyl ether, and poly (perfluoropropoxy). ) Fluorine-containing polyvinyl ether represented by vinyl ether, polyvinyl acetate, polyvinyl chloride or a copolymer thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin , Silicon resin and the like are exemplified, preferably,
Polymethyl methacrylate, fluorinated polymethacrylate, polyacrylate, fluorinated polyacrylate, polyolefin such as polystyrene, polyethylene, polypropylene, polybutene, polyvinyl ether, fluorinated polyvinyl ether and copolymers thereof, epoxy resin, Nafion and the like. . These polymer matrices can be used alone or as a mixture of two or more. In addition, these polymer matrices can be appropriately selected depending on the purpose, application, and the like.

As the method of dispersing or suspending the nano-sized (host-guest) complex of the present invention in a polymer matrix, a method known in the art can be used. For example, (1) a method of mixing a composite in a molten resin,
(2) A method in which the composite is dispersed in the polymer fine powder and then melted; (3) A method in which the monomer and the composite are thermally copolymerized using a polymerization initiator such as AIBN or lauroyl peroxide; (4) A casting method by removing the solvent after mixing the complex with the polymer solution, which is useful for preparing a polymer film,
(5) Spin coating method, (6) Co-evaporation method and the like.

Additives may be added to the composition containing the polymer matrix, if necessary, for the purpose of improving the properties of the polymer matrix, as long as the function is not impaired. Examples of such additives include phthalic acid diesters such as dibutyl phthalate and dioctyl phthalate, dibasic acid diesters such as dioctyl adipate, polyol esters such as pentaerythritol tetrabenzoate, rosin acid soap, stearic acid soap, and oleic acid. Soap, dispersant containing surfactant such as sodium lauryl sulfate, sodium diethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate or anionic antistatic agent such as alkyl sulfonate, alkyl ether carboxylic acid, polyethylene Nonionic antistatic agents such as glycol derivatives and sorbitan derivatives; cationic antistatic agents such as quaternary ammonium salts and alkylpyridium; talc, fatty acid metal salts; sorbitol-based crystallization nucleating agents; Phenolic antioxidants, thioether antioxidants such as Le hydroxy phenols,
Examples include phosphorus-based antioxidants, pigments, light stabilizers, crosslinking agents, crosslinking accelerators, flame retardants, processing aids, and the like. The amount of these additives is about 0.01 to 10 parts by weight based on 100 parts by weight of the polymer matrix.

In molding the composition containing the polymer matrix according to the present invention, for example, a method of re-melting and molding the composition containing the polymer matrix once prepared, or a method of preparing the composition containing the polymer matrix at the time of preparing the composition. There is a method of molding at the same time. Further, as the molding means, a known molding method can be used. For example, injection molding, extrusion molding, blow molding, compressed air molding, rotational molding,
Film forming and the like can be mentioned. Further, the nanosize (host-guest) composite of the present invention can be blended at a high concentration in a polymer matrix and extruded to form a masterbatch.

The shape of the molded body is not particularly limited, and may be appropriately selected depending on the purpose, application and the like. For example, rod shape,
Examples include films, plates, cylinders, circles, ellipses, and special shapes such as toys and ornaments, for example, a star shape and a polygonal shape.

In any of the above-described molding methods and molded articles, the molded article containing the resin composition according to the present invention has luminescence characteristics.

The composition containing the nano-sized (host-guest) complex of the present invention does not cause light scattering and can be used as an optical functional material. For example, it is useful for applications such as light-emitting materials, EL elements, optical fibers, and lenses.
D player, optical disk, facsimile, remote control,
Copy equipment, laser printers, large displays,
It can be used for optical devices such as medical lasers, laser processing measurement, and printing. Specifically, it can be applied to laser elements, light emitting diodes, liquid crystals, optical fibers, photodetectors, solar cells, and the like.

Further, by applying the present invention to various plastic products, it can be used as a light-emitting forming material whose contents or structure can be seen through.
It is also useful as a material for light reflectors of traffic lights or automobiles, various traffic signs, and as a material for luminous decorative articles.

[0146]

According to the present invention, the inorganic host compound includes
By supporting a rare-earth metal ion and / or a rare-earth metal complex as a guest compound and forming a (host-guest) composite having an average particle size of nano-size, the emission characteristics of the guest compound can be improved.

The nano-sized (host-guest) composite of the present invention has a high dispersing ability in a medium, and is uniformly dispersed without becoming cloudy in a medium, so that it can be suitably used as an optical functional material. .

[0148]

EXAMPLES Various experiments were carried out in order to explain the present invention in more detail. The present invention is not limited to these examples. The emission spectrum was measured by JASCO Corporation S
It measured using S-25. Production Example: L-type nano-sized zeolite 3.6 g of aluminum foil was added to 150 ml of 3M KOH solution to prepare a transparent potassium aluminate solution.
The solution was filtered to remove impurities from the aluminum foil. Then, fumed silica (80
g) was suspended in 300 ml of 3M KOH solution and heated under stirring at 80 ° C. for 12 hours. After cooling to room temperature, the clear potassium aluminate solution obtained above was slowly added to the above silicate solution with vigorous stirring to obtain a clear homogeneous solution. Subsequently, water and KOH solution were added to adjust the concentration. The obtained solution was transferred to a stainless steel container whose inside was coated with Teflon, and refluxed with stirring. The obtained solid was centrifuged (4000 G,
(2 hours), and the mixture was washed with water and centrifuged repeatedly until the pH of the supernatant was 8 or less. After drying at 110 ° C. for 12 hours, the average particle diameter was measured using DLS (ELS-800, manufactured by Otsuka Electronics Co., Ltd.).
Met. The Si / Al ratio was 2.6. (Reference: Chem. Master, Vol. 7, 1734-1741)
(Page, 1995) The other nano-sized zeolites (X-type and Y-type) used in the present invention were prepared by the same method. Example 1: Preparation of Eu3 ⁺ -supported L-type nanosize zeolite 0.2 g of L-type nanosize zeolite (Si / Al = 2.6, average primary particle size = 100 to 200 nm)
It was dispersed in 30 ml of MEu (NO ₃ ) ₃ and refluxed at 100 ° C. for 72 hours. After removing the unsupported Eu (NO ₃ ) ₃ by dialysis using cellophane, the concentration of Eu ³⁺ in the water removed by dialysis was confirmed by an electric conduction method, and repeated until the Eu ³⁺ concentration became 0. Dialysis was performed.
Subsequently, the aqueous layer containing the nano-sized zeolite was concentrated under reduced pressure to obtain a nano-sized zeolite powder, which was dried at 120 ° C for 12 hours. The obtained nano-sized zeolite is I
According to CP / MS analysis, (3Eu + K) /Al=1.06
And the ion exchange rate was 35%.

Furthermore, the above nano-sized zeolite (10 mg)
DMSO (3.0 ml) was added to the mixture and sonicated (5 minutes)
Dispersed the zeolite in DMSO. It was visually confirmed that it was transparent. Filtration was performed using a 0.45 μm filter, and the filtrate was subjected to DLS (Dyna).
mic Light Scattering, "DL"
S ”. ) Upon measurement, the average particle size of the nano-sized zeolite in DMSO was 190 nm.

The same result can be obtained when Tb ₄ O ₃ or YbCl ₃ is used in place of Eu (NO ₃ ) ₃ in the first embodiment. Example 2: Preparation of Eu3 ⁺ -supported X-type nanosize zeolite 0.2 g of X-type nanosize zeolite (Si / Al = 1.3, average particle size of primary particles = 50 to 100 nm) was added to 0.1 M
It was dispersed in 20 ml of Eu (NO ₃ ) ₃ and refluxed at 100 ° C. for 72 hours. After removing the unsupported Eu (NO ₃ ) ₃ by dialysis using cellophane, 0.0 was further added.
In 20 ml of 5MEu (NO ₃ ) ₃ , 100 ° C., 7
Refluxed for 2 hours. After the dialysis again, the same treatment as in the example was performed to obtain a Eu ³⁺ -supported X-type nano-sized zeolite powder. Further, the obtained nano-sized zeolite was
Dry at 12 ° C for 12 hours.

The obtained nano-sized zeolite was
When DLS measurement was performed by the same method as in Example 1, the average particle size of the nano-sized zeolite in DMSO was:
It was 62 nm.

The same result is obtained when Tb ₄ O ₃ or YbCl ₃ is used in place of Eu (NO ₃ ) ₃ in the second embodiment. Example 3: Emission spectrum The nano-sized zeolite obtained in Example 1 was converted to D ₂
Dispersed in O and left overnight. After D ₂ O was distilled off in a vacuum system, the obtained deuterated nano-sized zeolite was added to vacuum-distilled DMSO-d ₆ under a nitrogen atmosphere. The sample was freeze-degassed and redispersed by sonication (5 minutes). After standing for 12 hours to precipitate the zeolite that is not stably dispersed, a clear supernatant liquid (DMSO
-D ₆ dispersion) (excitation wavelength: 395 nm).

Further, the emission spectrum of the nano-sized zeolite obtained in Example 2 was measured in the same manner.

In each sample, 595, 6
An emission spectrum having an absorption maximum at 15, 650 and 695 nm was obtained, which was consistent with the emission spectrum of Eu ³⁺ . The emission intensity is DMS
It is stronger than the emission of Eu (NO ₃ ) ₃ of the same concentration in Od ₆ .

Further, the light emission lifetime of the sample obtained in Example 1 was 10 ms.

The emission spectrum of the sample obtained in Example 2 in DMSO-d ₆ is shown in FIG.

In the same manner as in Example 1, Eu ^{3+ was obtained} by using a commercially available inorganic layered compound such as hydrotalcite, numectite and montmorillonite, and a mesoporous material such as mesoporous silica FSM-16 instead of zeolite.
A supported nanosized (host-guest) complex is obtained.

Further, these rare earth metal ion-carrying inorganic (host-guest) composites have luminescence characteristics due to Eu ³⁺ . Example 4: Preparation of Eu (HFA) _3- supported X-type nanosize zeolite A glass container containing the Eu3 ⁺ -supported X-type nanosize zeolite obtained in Example 2 (0.5 g) was placed at 200 ° C for 2 hours. Vacuum degassing was performed to dehydrate zeolite adsorbed water and the like. Subsequently, HFA (hexafluoroacetylacetone, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a glass container at 0.5.
Then, after freezing and degassing under vacuum, the ion-supported zeolite was contacted with a volatile gas of HFA at room temperature for 24 hours. The white zeolite powder turned yellow. The obtained Eu (HFA) -supported zeolite was dispersed in cyclohexane, unreacted HFA was extracted into hexane, and the hexane layer was removed by centrifugation. After repeating this operation three times, the remaining cyclohexane was removed by drying under reduced pressure (non-heated sample).

Furthermore, the Eu (HFA) -supported zeolite was dried under vacuum at 165 ° C. for 2 hours to remove coordination water and bound water in the complex (heated sample). FIG. 3 shows IR charts of each sample before and after the heat treatment.

Thereafter, in the above-mentioned glass container, at 165 ° C.
For 30 minutes with heavy water vapor. Further, after degassing, the operation of contacting with heavy water vapor was repeated three times to perform heavy water replacement (heavy water replacement sample). Example 5: Emission spectrum of Eu (HFA) ₃ -supported X-type nanosize zeolite The emission spectrum of the powder was measured for the three samples obtained in Example 4. FIG. 4 shows the emission spectra of the unheated sample and the heated sample.

The light emission lifetime of each sample was as follows. Luminescence life of each sample of Eu (HFA) _3- supported X-type zeolite Sample Luminescence life / ms Unheated sample 0.29 Heated sample 0.46 Heavy water displacement sample 1.02 Sample with coordinating water removed (heated sample) The emission intensity was 1.7 times as high as that of the sample without heating (unheated sample). Further, the luminescence lifetime was longer than that of the complex alone.

That is, by replacing OH groups such as bound water in the zeolite and coordination water derived from the complex with OD groups,
Non-radiative deactivation in -H vibration was suppressed, and a longer life was possible.

The zeolite in the dispersion was further concentrated at a higher concentration.
(100 mg / ml), a clear composition is obtained. The UV-visible absorption spectrum (DMSO-d ₆ dispersion) of this dispersion is similar to that of the Eu (HFA) ₃ complex alone. Example 6: Preparation of Nd (CF ₃ SO ₂ NSO ₂ CF ₃ ) ₃ -supported Y-type nano-sized zeolite NdCl ₃ was used in place of Eu (NO ₃ ) ₃ in Example 1, and Y-type nano-sized zeolite was used. Zeolite
(Si / Al = 2.5, average particle size of primary particles = 60 to 90
nm) of 0.2 g was used to obtain a Nd ³⁺ -supported Y-type nano-sized zeolite. Using this zeolite, a commercially available CF ₃ SO ₂ NHSO ₂ CF ₃ (hereinafter abbreviated as “PMS”, manufactured by Fulka) is used, and in the same manner as in Example 4, Nd (PMS) ₃ -supported Y-type nanosize A zeolite was obtained. FIG. 5 shows the UV-VIS spectrum of the obtained composite. ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ; pp
m): -78.42 ppm When the obtained nano-sized zeolite was subjected to DLS measurement by the same method as in Example 1, the average particle size of the nano-sized zeolite in DMSO was 141 nm. Example 7: Nd (PMS) ₃ carrying Y-type nano-sized zeolite emission spectra obtained in Example 6 was Nd (PMS) ₃ carrying Y-type nano-sized zeolite in the same manner as in Example 3 DMSO-d
₆ and the luminescence yield was measured. As a result, Nd (PMS) ₃ not supported on nano-sized zeolite had an emission yield of 3.0%, whereas Nd (PMS) ₃ supported Y
The luminous yield of the nano-sized zeolite is 9.5%,
It was found that zeolite significantly suppressed vibrational deactivation and cross-deactivation.

[0164] Incidentally, the emission spectrum of Nd (PMS) ₃ carrying Y-type nano-sized DMSO-d ₆ in the zeolite in FIG.

Further, similar results are obtained when POS or PBS is used as the ligand. The method for synthesizing these ligands is described below as a reference example. Under nitrogen atmosphere, Example _{1 C 8 F 17 SO 2 NHSO} 2 C 8 F 17 (POS), C 8 F 17 SO to ₂ NHNa of 18mmol [(CH _{3) 3} Si] ₂ NH (18ml, _86.5mmo
l) was added dropwise. Add 2 ml of dioxane, and add
After refluxing for 8 hours, [(CH ₃ ) ₃ Si] ₂ NH was distilled off, followed by vacuum drying for 12 hours. 30 ml of dry acetonitrile and 21 mmol of C ₈ F ₁₇ SO ₂ F were added, and the mixture was refluxed at 100 ° C. for 48 hours. Thereafter, acetonitrile was distilled off, protonation was performed using sulfuric acid, and the target product (white solid, yield 1) was extracted by ether extraction and sublimation.
2%). IR (cm ^-1 ): 1373 (S = Ost.), 1237
(C-Fst.), 1206 (C-Fst.), 115
1 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ; pp
m): -79.51 (3F), -111.59 (2
F), -118.43 (2F), -120.10 (6
F), -121.06 (2F), -124.59 (2
F). Reference Example 2 Synthesis of C ₄ F ₉ SO ₂ NHSO ₂ C ₄ F ₉ (PBS) Instead of C ₆ F ₁₃ SO ₂ NHNa and C ₆ F ₁₃ SO ₂ F, C ₄ F ₉ SO ₂ NHNa and C ₄ were used, respectively. except for using F ₉ SO ₂ F was obtained with _{C 4 F 9 SO 2 NHSO 2} C 4 F 9 in the same manner as in reference example 1 (white solid, 26% yield). IR (cm ^-1 ): 1373 (S = Ost.), 1237
(C-Fst.), 1206 (C-Fst.), 115
1 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ; pp
m): -79.31 (6F), -111.47 (4
F), -119.18 (4F), -124.19 (4
F).

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing a relationship among a vibration frequency, a vibration overtone, and a vibration quantum resonating with an energy gap of Nd ³⁺ at a binding site of a molecule in the case of an Nd complex.

FIG. 2: DMS of Eu ³⁺ supported X-type nano-sized zeolite
Is a graph showing an emission spectrum in the O-d _6.

FIG. 3 shows a non-heated sample (3a) and a heated sample (3b) of Eu (HFA) ₃ -supported X-type nanosized zeolite.
FIG. 3 is a diagram showing an IR spectrum of the present invention.

FIG. 4 shows a non-heated sample of Eu (HFA) ₃ -supported X-type nanosize zeolite (indicated as “Before heating Eu (HFA) ₃ -X” in the figure) and a heated sample (“Eu (HFA) _{3 in the} figure”). (Displayed after -X heating)
And Eu ³⁺ supported X-type nano-sized zeolite (in the figure, “Eu
FIG. 2 is a diagram showing an emission spectrum of a powder (displayed as “-X”).

FIG. 5 is a view showing a UV-VIS spectrum of Nd (PMS) ₃ supported Y-type nano-sized zeolite.

FIG. 6 is a view showing an emission spectrum of Nd (PMS) ₃ supported Y-type nano-sized zeolite in DMSO-d ₆ .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 311/48 C07C 311/48 G01N 21/76 G01N 21/76 // C07F 5/00 C07F 5/00 B C09K 11/06 C09K 11/06 660 660 (72) Inventor Yasuya Hasegawa 13-Yoshimachi Yakuracho, Fushimi-ku, Kyoto, Kyoto New Japan Chemical Co., Ltd. F-term (reference) 2G054 AA10 CE10 EA01 EB01 GA02 GA03 GE01 4G073 BA14 BA69 BA70 BA72 BA73 BB58 BB61 BB67 CA06 CM09 CM15 CM22 CN04 CZ04 CZ05 CZ10 DZ04 UB37 4G076 AA01 AA18 AA19 AA22 AA24 AA26 AB02 AB12 AB13 AC02 BC07 BC08 BF10 BG06 CA02 CA05 CA12 CA26 CA33 CA40 DA30 4A00 A048 A02 VA30 VA40 VA45 VA70 VB10 VB20

Claims (17)

[Claims] 1. An inorganic host compound having at least one selected from the group consisting of a rare earth metal ion and a rare earth metal complex and having an average particle size of nano-sized (host-
Guest) complex. 2. A (host-guest) composite having an inorganic host compound and a rare-earth metal ion supported thereon and having an average particle size of nano-size. 3. An inorganic host compound carrying a rare earth metal complex and having an average particle size of nano-size (host-guest).
Complex. 4. The nano-sized (host-guest) composite according to claim 1, wherein the inorganic host compound is at least one selected from the group consisting of a zeolite, an inorganic layered compound, and a mesoporous material. body. 5. The nano-sized (host-guest) composite according to claim 1, which has an average particle diameter of 1 to 200 nm or less. 6. The nanoparticle according to claim 1, wherein the Frank-Condon constant derived from interatomic bonds of atoms constituting the rare earth metal complex is more than 0 and not more than 0.061. (Host-guest) complex of size. 7. The supported rare earth metal complex has a general formula
(I): [Wherein, M represents a rare earth atom, and n1 represents 2-4.
n2 represents 2, 3 or 4. Rf ¹ and Rf ² are the same or different and represent a C _1-22 aliphatic group, an aromatic group or a heterocyclic group, and X ¹ and X ² are the same or different and represent a group IVA atom, VA excluding nitrogen. V excluding group atoms and oxygen
It represents any of Group IA atoms, and n3 and n4 represent 0 or 1. Y represents CZ (Z represents a hydrogen, deuterium, halogen atom or C _1-22 aliphatic group, aromatic group, cyano group), N, P, Sb or Bi. ]: And the general formula (II) Wherein M, n1 and n2 are as defined above. Rf ³ represents a C _1-22 aliphatic group, aromatic group or heterocyclic group; X ³ represents any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen;
Represents 0 or 1. The nano-sized (host-guest) complex according to any one of claims 1 to 3, which is at least one selected from the group consisting of complexes represented by the following formula: 8. The supported rare earth metal complex has a general formula
(III): Wherein M, n1 and n2 are as defined above. Rf ⁴ and Rf ⁵ are the same or different and represent a C _1-22 aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom. The nano-sized (host-guest) complex according to any one of claims 1 to 3, which is a complex represented by the formula: 9. The supported rare earth metal complex has a general formula
(IV): Wherein M, Rf ⁴ , Rf ⁵ , n1 and n2 are as defined above. And a complex represented by the formula:
4. The nano-sized (host-guest) complex according to any one of claims 3 to 3. 10. The supported rare earth metal complex has a general formula (V): Wherein M, Rf ⁴ , Rf ⁵ , n1 and n2 are as defined above. Z ′ represents a deuterium, a C _1-22 aliphatic group containing no halogen or hydrogen atom, an aromatic group containing no hydrogen atom, and a cyano group. The nano-sized (host-guest) complex according to any one of claims 1 to 3, which is a complex represented by the formula: 11. A composition comprising the nanosized (host-guest) complex according to claim 1 dispersed in a solvent. 12. A composition comprising the nanosized (host-guest) composite according to claim 1 dispersed in a polymer matrix. 13. A molded article comprising the composition according to claim 11. 14. An optical functional material comprising the nano-sized (host-guest) composite according to claim 1. 15. A rare earth element selected from the group consisting of (a) an inorganic host compound having an average particle diameter of nano-size and (b) a rare earth metal oxide, a rare earth metal alkside, a rare earth metal amide and a rare earth metal salt. By stirring the solution of the metal compound, the rare-earth metal ion is supported on the inorganic host compound, and the average particle diameter supporting the rare-earth metal ion is nano-sized (host-guest).
A method for producing a composite. 16. A compound of the general formula (VI): [Wherein Rf ¹ , Rf ² , X ¹ , X ² , n3, n4 and Y
Is as defined above. ]: And the general formula (VI
I): embedded image Wherein Rf ³ , X ³ and n5 are as defined above. ], By vaporizing or sublimating at least one selected from the group consisting of compounds represented by the formula, the average particle diameter supporting rare earth metal ions is nano-sized
A method for producing a (host-guest) composite having a nano-size average particle diameter carrying a guest compound containing a rare-earth metal complex, wherein the (host-guest) composite forms a rare-earth metal complex. 17. A compound of the general formula (VI): [Wherein Rf ¹ , Rf ² , X ¹ , X ² , n3, n4 and Y
Is as defined above. ]: And the general formula (VI
I): Wherein Rf ³ , X ³ and n5 are as defined above. In a solution of the compound represented by the formula, by stirring the nano-sized (host-guest) complex supporting the rare-earth metal ion, the rare-earth metal complex in the (host-guest) complex The average particle diameter supporting a guest compound containing a rare earth metal complex characterized by forming a nano-sized (host-guest)
A method for producing a composite.