JP6159569B2 - Metal compound - Google Patents

Description

The present invention relates to a metal compound. More specifically, the present invention relates to a novel metal compound having a structure in which metal atoms and oxygen atoms are coordinated to have a specific arrangement.

A metal compound having a structure in which a metal atom and an oxygen atom are coordinated has different characteristics depending on the type of metal atom and its coordination state, and is expected to be used for various applications. Among them, metal compounds having one or more structures derived from a heteropolyoxometalate compound having a structure in which a polyatom is coordinated via oxygen to a heteroatom centered on a heteroatom include oxidation reactions and acid-base reactions. Some are known to be usable as catalysts for organic reactions.

The heteropolyoxometalate compound has a defect structure in which two atoms that should be in the structure of the Keggin type heteropolyoxometalate are missing, and two or more kinds of metal elements are present in the defect site. What is contained, that is, a disubstituted heteropolyoxometalate in which a poly atom is substituted with two or more other metal elements is a monosubstituted heteropolyoxometalate or a trisubstituted heteropolyoxometalate It is known that it exhibits a specific oxidation catalyst activity as compared to (see Non-Patent Document 1). For a disubstituted polyoxometalate in which Ti is introduced into the two-deficient structure site of the heteropolyoxometalate where the hetero element is silicon, the compound is a two-deficient polyoxometalate with two Ti atoms and two oxygen atoms. It has been clarified by X-ray crystal structure analysis that it has a structure dimerized through atoms (see Non-Patent Document 2).

Heteropolyoxometalate anions having two- and / or three-defect structural sites, vanadium, tantalum, niobium, antimony, bismuth, chromium, molybdenum, selenium, tellurium, rhenium, cobalt, nickel, ruthenium, rhodium, palladium A catalyst containing at least one element selected from the group consisting of osmium, platinum, iridium, silver, gold, zinc, aluminum, gallium, indium, scandium, yttrium, titanium, zirconium, hafnium, germanium, tin and lanthanoids, It is disclosed that the target epoxy compound can be obtained by oxidizing an ethylenic double bond with an oxidizing agent (see Patent Document 1). In addition, an element selected from the group consisting of nickel, palladium, iridium, and platinum of rare earth, group 4, group 5, group 6, group 7, group 9, and group 10 is used as the defect site in the two-deficient polyoxometalate. It is disclosed that the target epoxy compound can be obtained by introducing and oxidizing the ethylenic double bond with oxygen (see Patent Document 2).

International Publication No. 02/072257 JP 2003-64007 A

Y. Nishiyama, Y. et al. Nakagawa, N .; Mizuno, “Ange. Chem. Int. Ed.” (Germany), 2001, vol. 40, p. 3639. Y. Goto, K.K. Kamata, K .; Yamaguchi, K .; Uehara, S .; Hikichi, N .; Mizuno, “Inorg. Chem.” (USA), 2006, 45, p. 2347.

As described above, polyoxometalate compounds having various structures are known. Polyoxometalates, which are anionic clusters of early transition metal oxides with various structures, are highly stable and have various chemical and physical properties that can be easily adjusted. It is an attractive substance in the field. For this reason, development of a polyoxometalate compound having a new structure has been demanded.
This invention is made | formed in view of the said present condition, and aims at providing a promising new metal compound as a new functional material.

The present inventor has investigated a metal compound containing at least one structural site derived from a heteropolyoxometalate compound containing a deficient structural site having a structure in which a poly atom is coordinated to a hetero atom via an oxygen atom, A new metal compound was found. Each of these compounds has a structural site derived from a heteropolyoxometalate compound containing at least one defective structural site selected from the group consisting of one defective structural site, two defective structural sites, and three defective structural sites. And a metal compound having a specific element which is a metal atom different from the hetero atom and the poly atom. A metal compound having such a structural feature has not been known so far, and is a metal compound having a novel structure that has been found for the first time in the present invention.
The present inventors have found that a metal compound having such a structural feature is a promising compound expected to be used as a magnetic material or the like, and has reached the present invention.

That is, the present invention relates to a metal compound having at least one structural site derived from a deficient structural site-containing heteropolyoxometalate compound, wherein the heteropolyoxometalate compound has a poly atom via an oxygen atom with respect to a hetero atom. The metal compound has a coordinated structure, and the metal compound is a structural site derived from a heteropolyoxometalate compound containing at least one defective structural site selected from the group consisting of one defective structural site, two defective structural sites, and three defective structural sites The heteropolyoxometalate compound containing a metal atom different from a heteroatom and a polyatom, wherein the one-deficient or two-deficient structure site-containing heteropolyoxometalate compound is selected from the group consisting of P, Si, Ge and Zn And the three-deficient structure site-containing heteropolyoxometalate compound includes P, Si and Including at least one heteroatom selected from the group consisting of Ge, wherein the metal atom is at least one atom selected from the group consisting of lanthanoid, Mn, Fe, Co, Ni, Cu, Ag, Zn It is a metal compound characterized by being.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The metal compound of the present invention is a metal compound containing at least one structural site derived from a heteropolyoxometalate compound containing a deficient structural site having a structure in which a poly atom is coordinated to an hetero atom via an oxygen atom.
Defect structure site-containing heteropolyoxometalate compound having a large negative charge has a high affinity for metal cations, so it can be used as a polydentate ligand to obtain a structure site derived from a defect structure site-containing heteropolyoxometalate compound And a mononuclear or polynuclear metal oxide core sandwiched between the structural sites can be synthesized. Utilizing these metal nuclei, heteropolyoxometalate compounds exhibit unique catalytic, photochemical, electrochemical and magnetic properties.

As long as the structure site derived from the defect structure site-containing heteropolyoxometalate compound is derived from the defect structure site-containing heteropolyoxometalate compound, the structure of the defect structure site-containing heteropolyoxometalate compound is retained as it is. The structure of the defect structure site-containing heteropolyoxometalate compound may be changed. In addition, the number of structural sites derived from the defect structure site-containing heteropolyoxometalate compound is not particularly limited as long as it is 1 or more, but it has two or more structure sites derived from the defect structure site-containing heteropolyoxometalate compound. Is one of the preferred embodiments of the present invention.
In addition, the structure part derived from the deficient structure part-containing heteropolyoxometalate compound is a part of the structure of the deficient structure part-containing heteropolyoxometalate compound, and is a structure composed of heteroatoms, polyatoms and oxygen atoms. It is a part.

The defect structure site-containing heteropolyoxometalate compound has at least one defect structure site selected from the group consisting of one defect structure site, two defect structure sites, and three defect structure sites. The metal compound of the present invention has at least one structural site derived from a defect structure site-containing heteropolyoxometalate compound, but when having two or more, the structure sites derived from these plurality of defect structure site-containing heteropolyoxometalate compounds are The number of poly atom defects may be the same or different. Preferably, the number of poly atom defects is the same.

Of the deficient structure site-containing heteropolyoxometalate compound, the 1-deficient or 2-deficient structure site-containing heteropolyoxometalate compound contains at least one heteroatom selected from the group consisting of P, Si, Ge and Zn. The three-deficient structure site-containing heteropolyoxometalate compound contains at least one heteroatom selected from the group consisting of P, Si and Ge.
Among the structural sites derived from the one-deficient or two-deficient structural site-containing heteropolyoxometalate compound, the structural site of the metal compound of the present invention is more preferably a structural site derived from the two-deficient structural site-containing heteropolyoxometalate compound. is there. Moreover, as a hetero atom which the structural part derived from a 1 deficient or 2 deficient structure part containing heteropolyoxometalate compound has, at least 1 sort (s) of an atom selected from the group which consists of P, Si, and Ge is preferable.

The metal compound of the present invention has at least one atom selected from the group consisting of lanthanoids, Mn, Fe, Co, Ni, Cu, Ag, and Zn as metal atoms different from heteroatoms and polyatoms. is there.
When the polynuclear metal compound of the present invention has a structural site derived from a single-deficient or double-deficient structural site-containing heteropolyoxometalate compound, the metal atoms different from heteroatoms and polyatoms include lanthanoids, Mn, Fe, Co, At least one atom selected from the group consisting of Ni, Cu, Ag and Zn is preferred. More preferably, at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Mn, Fe, Co, Ni, Cu, Ag, Zn Is an atom.
When the metal compound of the present invention has a structural site derived from a three-deficient structural site-containing heteropolyoxometalate compound, the metal atoms different from heteroatoms and polyatoms include lanthanoids, Mn, Fe, Co, Ni, Cu, At least one atom selected from the group consisting of Ag and Zn is preferred. More preferably, at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Mn, Fe, Co, Ni, Cu, Ag, Zn Is an atom.
The metal compound of the present invention may have one type of metal atom different from the hetero atom and the poly atom, or may have two or more types, but the metal compound of the present invention may have a hetero atom and a poly atom. In the case of having two or more lanthanoid atoms as metal atoms different from atoms, a heteronuclear metal compound having two or more kinds of metal atoms is preferable from the viewpoint of characteristics as a magnetic material described later. More preferably, it is a heteronuclear metal compound having two or more lanthanoid atoms.
Among the above compounds, the metal compound of the present invention preferably has one or two metal atoms different from heteroatoms and polyatoms.

In the metal compound of the present invention, the poly atom is preferably at least one atom selected from the group of elements of Groups 5 and 6 of the periodic table. Examples of elements in Groups 5 and 6 of the periodic table include V, Nb, Ta, Cr, Mo, and W. Among these, at least one atom selected from the group consisting of V, Mo, and W is more preferable.

In the metal compound of the present invention, at least one of the metal atoms is coordinated with only one poly atom per structural site derived from one heteropolyoxometalate compound via one oxygen atom, and any one of the above The metal atom also has a structure in which the metal atoms are coordinated via one oxygen atom (hereinafter referred to as structure a), and at least one of the metal atoms has two or more heteropolyoxometalates. Coordinate via a poly atom and one oxygen atom in the structural site derived from the compound, and coordinate via two or more poly atoms and one oxygen atom per structural site derived from one heteropolyoxometalate compound Structure (hereinafter referred to as structure b), a structure in which the four metal atoms are directly bonded to each other with at least two other metal atoms (hereinafter referred to as structure c), and four The metal atoms are mutually one through an oxygen atom coordinated to three other metal atomic structure (hereinafter, the structure d and described) is preferably one having at least one structure selected from. In addition, the metal atom here is a metal atom different from the hetero atom and the poly atom.

In the structure a, (metal atom-oxygen atom- polyatom ) is arranged between the heteroatom and polyatom constituting the metal compound and the structural site derived from the heteropolyoxometalate compound. the position coupling, one hetero polyoxometalate compounds derived structural moiety per only have metal atoms (hereinafter, also referred to as metal atom a) exists, and also between each other any metal atom (metal atom -Oxygen atom-metal atom).
The metal compound having the structure a may have at least one metal atom a, but the number of metal atoms a is preferably 2 to 4.

In the structure b, a metal atom different from a heteroatom and a polyatom has a (metal atom-oxygen atom- polyatom ) coordinate bond between two or more heteropolyoxometalate compound-derived structural sites. And a metal atom (hereinafter also referred to as metal atom b) having two or more coordination bonds (metal atom-oxygen atom- polyatom ) per structural site derived from one heteropolyoxometalate compound At least one structure exists. Therefore, the metal compound of structure b has at least four coordinate bonds of (metal atom-oxygen atom- polyatom ).
In the metal compound having the structure b, the number of metal atoms b is preferably 1 to 4. The metal atom b has two or more coordination bonds (metal atom-oxygen atom- polyatom ) per structural site derived from one heteropolyoxometalate compound, but preferably has 2-4.
In addition, the metal compound having the structure b may have a metal atom other than the metal atom b, and the coordinate bond of (metal atom-oxygen atom- polyatom ) is derived from two or more heteropolyoxometalate compounds. A metal atom having only one (metal atom-oxygen atom- polyatom ) coordination bond to the structural site derived from one heteropolyoxometalate compound. May be included.

The structure c has the following general formula (1);

(Wherein M is the same or different and represents a metal atom different from a hetero atom and a poly atom). In addition, the metal atom M which comprises the structure represented by the said General formula (1) may couple | bond with another metal atom.
The structure d is, for example, the following general formula (2-1) or (2-2);

(Wherein M is the same or different and represents a metal atom different from a hetero atom and a poly atom. O represents an oxygen atom), but is limited to these structures. Not. In addition, the metal atom M which comprises the structure represented by the said general formula (2-1), (2-2) may further couple | bond with another metal atom or oxygen atom.

The metal compound preferably includes at least one of the structures a to d, but may include two or three or more of these structures a to d.

The total content of metal atoms different from heteroatoms and polyatoms in the metal compound of the present invention is preferably more than one for one heteroatom in the metal compound. More preferably, it is 1.2 or more, and still more preferably 1.5 or more. Moreover, it is preferable that it is eight or less. More preferably, it is 7 or less, and more preferably 6 or less.
Moreover, it is preferable to have 1-8 metal atoms different from a hetero atom and a poly atom in the whole metal compound. More preferably, it is 1-6.
When the metal compound of this invention has the said structure a, it is preferable to have 2-4 metal atoms different from a hetero atom and a poly atom in the whole metal compound.
When the metal compound of this invention has the said structure b, it is preferable to have 1-6 metal atoms different from a hetero atom and a poly atom in the whole metal compound.
When the metal compound of this invention has the said structure c, it is preferable to have 4-6 metal atoms different from a hetero atom and a poly atom in the whole metal compound.
When the metal compound of this invention has the said structure d, it is preferable to have 4-6 metal atoms different from a hetero atom and a poly atom in the whole metal compound.

Among the metal compounds of the present invention, two or more structural sites derived from a heteropolyoxometalate compound are present, and a metal atom different from a heteroatom and a polyatom is bonded to a portion connecting these structural sites. A compound having only one compound is also called a mononuclear metal compound, and a compound having two or more metal atoms different from heteroatoms and polyatoms is also called a polynuclear metal compound.

The metal compound of the present invention has at least one structural site derived from a defective structural site-containing heteropolyoxometalate compound, but preferably has two structural sites derived from a defective structural site-containing heteropolyoxometalate compound. .

The metal compound of the present invention has a polyoxometalate in which a poly atom is coordinated through an oxygen atom (isopolyoxometalate) or a structure in which a poly atom is coordinated through an oxygen atom to a hetero atom. A heteropolyoxometalate compound having a structure in which a metal atom different from the heteroatom and polyatom is introduced as an element (B) into a deficient structure site of a deficient structure site-containing heteropolyoxometalate anion (A) Alternatively, it can be obtained by dissolving a compound having such a structure in a specific solvent.

In the heteropolyoxometalate compound, the element (B) is introduced into the deficient structure site of the heteropolyoxometalate anion (A). The introduction into the deficient structure site may be a form in which the element (B) is incorporated into the deficient structure site, that is, a form in which the poly atom to be present is replaced by the element (B). ) May have a coordinated form without incorporating the element (B) into the defect structure site.
The heteropolyoxometalate anion (A) has at least one deficient structure site selected from the group consisting of one deficient type, two deficient types, and three deficient types, and these deficient structures and heteroatoms, Preferred combinations of polyatoms and metal atoms different from heteroatoms and polyatoms are as described above.
Among these, the metal compound of the present invention is preferably one having a two-deficient structure or a three-deficient structure.

The heteropolyoxometalate compound is not particularly limited, such as a Keggin type or a Dawson type, but is preferably a Keggin type heteropolyoxometalate compound.
Moreover, as arrangement | positioning of an element (B), it is preferable that an element (B) mutually adjoins. The isomers in which the element (B) is adjacent to each other include α, β, γ, δ, ε isomers, etc., but the α, β isomers are isomers sharing a corner, and the γ, δ, ε isomers are It is an isomer with shared ridges. More preferably, the element (B) is introduced into the skeleton of at least one deficient structure site-containing Keggin heteropolyoxometalate anion selected from the group consisting of α-form, β-form and γ-form, Among these, the form most preferably introduced is the α-form and / or the γ-form deficient structure site-containing Keggin heteropolyoxometalate anion. That is, in the present invention, the defect structure site-containing heteropolyoxometalate compound is preferably at least one selected from the group consisting of α-form, β-form and γ-form. More preferably, the deficient structure site-containing heteropolyoxometalate compound is a two-deficient structure site-containing heteropolyoxometalate compound and is a γ-form, or a three-deficient structure site-containing heteropolyoxometalate compound. In addition, it is an α form.
The structure of such a heteropolyoxometalate compound is determined or estimated from X-ray crystal structure analysis, elemental analysis, UV, XRD, FT-IR spectroscopy, or the like.
As described above, the metal compound of the present invention is also a preferred embodiment of the present invention in which the heteropolyoxometalate anion (A) is an α-type and / or γ-type Keggin-type heteropolyoxometalate anion. One.

The heteropolyoxometalate compound generally forms a salt, and the cation source in producing the salt may be an inorganic salt or an organic salt. Among them, an alkali metal salt, an alkaline earth salt, a transition metal salt, Typical metal salts, proton salts, ammonium salts, organic ammonium salts, organic phosphonium salts, and the like are suitable. For example, the salt is contained in a liquid in which the heteropolyoxometalate anion (A) and the element (B) coexist. Is added as a powder or as a solution to produce the heteropolyoxometalate compound. The cation originally possessed by the heteropolyoxometalate anion (A) or the element (B) may be used.

The heteropolyoxometalate anion (A) is a heteropolyoxometalate anion having a deficient structure site lacking a poly atom to be present in the crystal structure, and the hetero atom is composed of silicon, phosphorus, germanium and zinc It is preferable that at least one selected from the group and at least one selected from the group consisting of molybdenum, tungsten, vanadium, and niobium. Such a heteropolyoxometalate anion (A) has a crystal structure called a Keggin type in which 9 to 11 polyatoms are coordinated to heteroatoms via oxygen.

The heteropolyoxometalate anion (A) in the two-deficient structure site-containing heteropolyoxometalate compound is represented by the following general formula (3);
[QZ ₁₀ O _j ] ^k- (3)
(In the formula, Q represents a hetero atom such as silicon, phosphorus, germanium, or zinc atom. Z represents a poly atom. J and k are positive numbers, and k is determined by the valences of Q and Z. It is preferably a Keggin type heteropolyoxometalate anion represented by
The heteropolyoxometalate anion (A) in the heteropolyoxometalate compound containing the three-deficient structure site is represented by the following general formula (4);
[QZ ₉ O _m ] ^n- (4)
(Wherein Q represents a silicon, phosphorus or germanium atom which is a hetero atom. Z represents a poly atom. M and n are positive numbers, and n is determined by the valence of Q and Z). The represented Keggin type heteropolyoxometalate anion is preferable.

Here, in the general formulas (3) and (4), a Keggin heteropolyoxometalate anion in which Z is tungsten is more preferable.
That is, it is also one of preferred embodiments of the present invention that the metal compound is a heteropolyoxometalate compound in which the hetero atom is a silicon, phosphorus, or germanium atom and the poly atom is tungsten.

Furthermore, the Keggin heteropolyoxometalate anion preferably has an isomer structure of α-form and / or β-form and / or γ-form. In the case of a heterogeneous structure-containing heteropolyoxometalate compound, more preferably, [α-PW ₁₀ O ₃₆ ] ^7- and / or [β-PW ₁₀ , wherein Q in the general formula (3) is phosphorus, silicon, or germanium. O ₃₆ ] ^7- and / or [γ-PW ₁₀ O ₃₆ ] ^7- , or [α-SiW ₁₀ O ₃₆ ] ^8- and / or [β-SiW ₁₀ O ₃₆ ] ^8- and / or [γ- SiW ₁₀ O ₃₆ ] ⁸⁻ , or [α-GeW ₁₀ O ₃₆ ] ⁸⁻ and / or [β-GeW ₁₀ O ₃₆ ] ⁸⁻ and / or [γ-GeW ₁₀ O ₃₆ ] ⁸⁻ . More preferably, [γ-PW ₁₀ O ₃₆ ] ⁷⁻ , [γ-SiW ₁₀ O ₃₆ ] ⁸⁻ or [γ-GeW ₁₀ O ₃₆ ] ⁸⁻ .
In the case of a heteropolyoxometalate compound containing a three-deficient structure site, more preferably, [α-PW ₉ O ₃₄ ] ^9- and / or [β- in which Q in the general formula (4) is phosphorus, silicon, or germanium. PW ₉ O ₃₄ ] ^9- and / or [γ-PW ₉ O ₃₄ ] ^9- , or [α-SiW ₉ O ₃₄ ] ^10- and / or [β-SiW ₉ O ₃₄ ] ^10- and / or [ γ-SiW ₉ O ₃₄ ] ¹⁰⁻ , or [α-GeW ₉ O ₃₄ ] ¹⁰⁻ and / or [β-GeW ₉ O ₃₄ ] ¹⁰⁻ and / or [γ-GeW ₉ O ₃₄ ] ¹⁰⁻ . .
More preferably, [α-PW ₉ O ₃₄ ] ^9- , [α-SiW ₉ O ₃₄ ] ^10- or [α-GeW ₉ O ₃₄ ] ^10- , and most preferably Q is phosphorus or silicon. [Α-PW ₉ O ₃₄ ] ^9- or [α-SiW ₉ O ₃₄ ] ^10- .

Examples of the counter cation that forms a salt with the heteropolyoxometalate anion include proton; alkali metal cation; alkaline earth cation; transition metal cation; typical metal cation; quaternary ammonium salt (ammonium salt, tetramethylammonium salt). , Tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt, benzyltriethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, cetylpyridinium salt ) And quaternary phosphonium salts (tetramethylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, tetrapheny Phosphonium salts, ethyltriphenylphosphonium salts, and organic cation benzyl triphenylphosphonium salt) and the like are preferable. Among these, an organic cation of a quaternary alkyl ammonium salt is more preferable. As the quaternary alkyl ammonium salt, an alkyl group having 4 to 48 carbon atoms is preferable. More preferably, it is 4-40.

Examples of the quaternary alkyl ammonium salt include tetramethyl ammonium salt, tetraethyl ammonium salt, tetrapropyl ammonium salt, tetrabutyl ammonium salt, tributyl methyl ammonium salt, trioctyl methyl ammonium salt, trilauryl methyl ammonium salt, and benzyl trimethyl ammonium salt. Benzyltriethylammonium salt, benzyltributylammonium salt, cetylpyridinium salt and the like. Among these, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, and benzyltributylammonium salt are preferable. More preferred are tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, and benzyltriethylammonium salt. Particularly preferred is a tetrabutylammonium salt.
One or more counter cations can be used.

What is preferable as the metal atom different from the hetero atom and the poly atom in the element (B), that is, the metal compound of the present invention is as described above.
The form used when introducing the element (B) may be a salt form or an oxide form. These may be inorganic or organic, but oxides, nitrates, halide salts, lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, barium salts, proton salts, ammonium salts, tetra Methyl ammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, carboxylate compound, acetate compound, acetylacetonate compound and the like are suitable.

The molar amount of the compound containing the element (B) used for the synthesis of the metal compound of the present invention is preferably more than 1 mol per 1 mol of the heteropolyoxometalate anion (A). More preferably, it is 1.1 mol or more, More preferably, it is 1.5 mol or more. Moreover, it is preferable that it is 8 mol or less. More preferably, it is 7 mol or less, More preferably, it is 6 mol or less.

The production method of the metal compound of the present invention is not particularly limited as long as it has the structure as described above. However, as a suitable production method, the element (B) is added to the heteropolyoxometalate anion (A). When introducing, it may be mixed in an organic solvent or a solvent containing an organic solvent. When mixed in an organic solvent or a solvent containing an organic solvent, unlike the case of mixing in water, the heteropolyoxometa having a novel structure in which the metal atom and oxygen atom of the present invention are in a specific positional relationship. A rate compound is obtained.
In addition to the mixing of the element (B), an acid may be added as described later. In addition, after adding the element (B) and introducing the element (B) into one heteropolyoxometalate anion (A), the heteropolyoxometalate anion (A) is further added to form a metal compound. Can be used.
In addition, in the solution obtained by dissolving the compound obtained by introducing the element (B) into one heteropolyoxometalate anion (A) in an organic solvent or a solvent containing an organic solvent, the one heteropolyoxometalate anion (A It is also possible to use a method of adding a compound obtained by introducing the element (B) into a metal compound by further adding a compound obtained by adding a poor solvent thereto. In addition, as long as the solvent containing the said organic solvent contains the organic solvent, it may contain other components, However, As one of the preferable forms of the solvent containing the said organic solvent, it is a mixed solvent of an organic solvent and water. The form is mentioned.

The volume ratio of the organic solvent and water in the mixed solvent of the organic solvent and water is not particularly limited, but is preferably 100: 0 to 30:70, and more preferably 100: 0 to 50: 50. More preferably, it is 100: 0 to 70:30.

The organic solvent is not particularly limited. For example, acetone, acetonitrile, benzonitrile, methanol, ethanol, propanol, butanol, chloroform, dichloroethane, hexane, octane, benzene, toluene, xylene, ethyl acetate, acetic acid. It is possible to use one or more of butyl, propylene carbonate, diethyl ether, dibutyl ether, diisopropyl ether, dioxane, tetrahydrofuran, cyclopentyl methyl ether, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, nitromethane, etc. it can. Among these, acetone, acetonitrile, benzonitrile, methanol, ethanol, butanol, dichloroethane, hexane, octane, toluene, xylene, ethyl acetate, butyl acetate, propylene carbonate, diethyl ether, dioxane, tetrahydrofuran, cyclopentyl methyl ether, methyl ethyl ketone, methyl Isobutyl ketone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, nitromethane are preferred, acetone, acetonitrile, benzonitrile, methanol, ethanol, butanol, dichloroethane, toluene, xylene, ethyl acetate, butyl acetate, propylene carbonate, diethyl ether, dioxane, tetrahydrofuran , Methyl ethyl ketone, methyl isobutyl ketone Dimethylformamide, dimethyl sulfoxide, nitromethane is preferable. Particularly preferred are acetone, acetonitrile, benzonitrile, butanol, toluene, ethyl acetate, butyl acetate, propylene carbonate, dichloroethane, diethyl ether, methyl isobutyl ketone, dimethylformamide, dimethyl sulfoxide, and nitromethane.

Examples of the poor solvent include hexane, octane, benzene, toluene, xylene, ethyl acetate, butyl acetate, propylene carbonate, diethyl ether, dibutyl ether, diisopropyl ether, dioxane, tetrahydrofuran, cyclopentyl methyl ether, methyl ethyl ketone, methyl isobutyl ketone, dichloroethane, One type or two or more types such as chloroform can be used.

The volume of the solvent is preferably 0.1 mL or more with respect to 1 mmol of the heteropolyoxometalate anion (A). More preferably, it is 0.5 mL or more, More preferably, it is 1.0 mL or more. Moreover, it is preferable that it is 300 mL or less. More preferably, it is 250 mL or less, More preferably, it is 200 mL or less.

The element (B) is added by adding the salt or compound of the element (B) as a powder or as a solution to a solution or mixed solution containing the heteropolyoxometalate anion (A). However, it may be added at the same time as (A) or may be carried out in the state of being dissolved in a solvent first. The element (B) salt or compound may be added all at once or gradually. The production of the heteropolyoxometalate compound may be performed in a single step or may be performed in multiple steps. For example, the product may be once taken out while leaving a part of the predetermined amount of (B), the product is redissolved in a solvent, and then the remaining (B) is added.

The mixing time of the heteropolyoxometalate anion (A) and the element (B) is preferably 1 minute or longer. When the mixing is performed for less than 1 minute, the element (B) may not be completely introduced into the defect site of the heteropolyoxometalate anion (A). More preferably, it is 10 minutes or more, More preferably, it is 20 minutes or more. Moreover, it is preferable that it is within 72 hours. More preferably, it is within 48 hours, and further preferably within 24 hours.
Note that the mixing time of 1 minute or more means the time during which coexistence and mixing of the element (B) and the solvent in the homogeneous solution mainly when 0.34 mmol of the heteropolyoxometalate anion (A) is used. Meaning, from the time when the addition of the salt or compound containing the element (B) to the solution or mixture containing the heteropolyoxometalate anion (A) is completed, the addition of the inorganic salt or organic salt to the above It refers to the time between when the telopolyoxometalate compound is precipitated. If precipitation of impurities or the like occurs during mixing, it can be removed as necessary. The setting of the mixing time is one of important elements for determining the structure of the heteropolyoxometalate compound, and may be appropriately selected within the above range depending on the type of the element (B). Heteropolyoxometalate compounds can be purified by recrystallization or the like. Moreover, preparation, storage, application as a catalyst or material, etc. can be performed in the system without isolation.

The temperature at which the heteropolyoxometalate anion (A) and the element (B) are mixed is preferably 0 ° C. or higher and 150 ° C. or lower. More preferably, it is 5 degreeC or more and 100 degrees C or less, More preferably, it is 10 degreeC or more and 90 degrees C or less.

An acid may be further added when the element (B) is introduced into the heteropolyoxometalate anion (A). The acid may be added after the salt or compound containing the element (B) is added, or may be added together with the salt or compound containing the element (B), but the salt or compound containing the element (B) is added. It is preferable to add after.
As the acid, in addition to inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, organic acids such as p-toluenesulfonic acid, acetic acid, benzoic acid and malonic acid can be used.
The amount of acid added is preferably 0.0001 mol or more per 1 mol of the heteropolyoxometalate anion (A). More preferably, it is 0.001 mol or more.

The metal compound of the present invention is manufactured by a multi-step manufacturing method in which a compound corresponding to the metal compound of the present invention is manufactured by the above-described method, and then another operation is performed on the metal compound. It may be a thing. By such a multistage production method, a metal compound containing two or more metal atoms different from hetero atoms and poly atoms, or a metal compound having a specific structure can be produced.

In addition, the obtained heteropolyoxometalate compound (metal compound) is dissolved in an organic solvent, a counter cation is added and stirred, and then the solid content obtained by removing the solvent is recrystallized in the presence of a specific organic solvent. A multi-stage manufacturing method is also suitable. By such a production method, a metal compound in which metal atoms have a specific arrangement such as a cubane type can be produced.

Moreover, after manufacturing the metal compound which has 1 type of metal atoms different from a hetero atom and a poly atom, the said metal compound is melt | dissolved in an organic solvent, and the metal different from the metal atom which the said metal compound has in the obtained solution is obtained. A multistage production method for producing a metal compound having two or more metal atoms by adding and stirring an atomic compound is also suitable. By such a production method, a metal compound having two or more metal atoms different from hetero atoms and poly atoms can be produced. In particular, such a multistage production method is a very useful production method in that a compound having two or more metal atoms different from hetero atoms and poly atoms can be selectively produced. When such a method is used, a metal compound having a heteronuclear lanthanoid structure containing two or more lanthanoids, for which no synthetic method has been developed, can be produced.
Further, the metal atoms can be arranged in the specific arrangement by a multi-stage production method.
As will be described later, the metal compound of the present invention has properties as a magnetic material (monomolecular magnet). Among them, a monomolecular magnet made of a lanthanoid metal has a large energy barrier due to a large magnetic anisotropy derived from the ground state of the spin-orbit coupled lanthanoid metal, and may have a high operating temperature. Except for some binuclear structures with radical bridging ligands, most lanthanoid complexes show very weak magnetic interactions. Therefore, in order to obtain a large magnetic anisotropy, designing the coordination structure of each lanthanoid cation is very important in designing a monomolecular magnet. Since the polyoxometalate having a heteronuclear lanthanoid structure can also be produced by using the multi-stage production method, the production method is very useful in designing a monomolecular magnet having a lanthanoid cation. .

The organic solvent used in the second and subsequent operations in the case of producing a metal compound by the above-described multistage production method is not particularly limited in addition to the above organic solvent, but dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone, propylene carbonate, nitromethane, acetonitrile, diethyl ether, and ethyl acetate, and one or more of these can be used. Among these, dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene carbonate, nitromethane, acetonitrile, diethyl ether, and ethyl acetate are preferable. More preferred are dimethylformamide, dimethylacetamide, acetone, nitromethane, acetonitrile, diethyl ether, and ethyl acetate.

When two or more organic solvents are used during the production of the metal compound of the present invention, the ratio is not particularly limited, but when two organic solvents are used, the ratio of the two organic solvents is 99/1 to 1/99. It is preferable to use in. If such a ratio is deviated, the effect of using two kinds of solvents may not be sufficiently exhibited. More preferably, the ratio is 90/10 to 10/90.

The metal compound of the present invention can be used as a magnetic material (single molecular magnet) because of its magnetic properties, and is used in various fields where magnetic materials are used, such as high-density information recording materials and data processing devices. It is a promising compound expected to be used.

The metal compound of the present invention can also be applied as a catalyst for organic reactions such as various oxidation reactions and acid-base reactions. When the heteropolyoxometalate compound of the present invention is used as a catalyst, it can be used in any reaction field such as a gas phase, a liquid phase, and a supercritical phase. As a usage form, when used in a gas phase reaction, a form in which the reaction is carried out with the catalyst itself as a solid or a form in which the reaction is carried by supporting the catalyst on a carrier is possible. As the catalyst carrier, a carrier generally used for gas-solid reaction can be used.
When the catalyst itself is used as a solid, the same counter cation as that described above can be used.
Moreover, when using by liquid phase reaction, the form which dissolves a catalyst and makes it react in a homogeneous system, and the form which suspends in a liquid phase and does not dissolve a catalyst in a solvent are mentioned. It is also possible to carry out the reaction using the catalyst as a solid phase. At this time, the catalyst itself can be used as a solid by changing the counter cation and the solvent, and separation of the catalyst and the product after the reaction is facilitated.

In addition, the catalyst can be used as a solid phase by supporting the catalyst on a carrier. As the catalyst carrier, carriers generally used for heterogeneous reactions such as various ion exchange resins, silica, alumina, titania, zirconia, tin oxide and other oxides can be used. In carrying out the reaction in a homogeneous system and / or a heterogeneous system, the same countercation as described above can be used.

The metal compound can be applied as a catalyst for organic reactions such as various oxidation reactions and acid-base reactions. Among them, it can be suitably applied when performing oxidation reactions and acid-base reactions in a liquid phase. It can be done.

Specific examples of the oxidation reaction are not particularly limited. For example, (1) oxidation of unsaturated bond (oxidation of unsaturated double bond or unsaturated triple bond of alkene or alkyne), (2) oxidation of hydroxyl group, ( 3) Oxidation of heteroatoms (oxidation of sulfur atoms, nitrogen atoms, silicon atoms, etc.), (4) Oxidation of saturated hydrocarbon sites, (5) Oxidation of aromatic rings, (6) Hydroxy heteroatoms and hydroxyl groups of hydrocarbons (Hydroxylation of hydrides such as sulfur atom, nitrogen atom, silicon atom) (7) Oxidation reactions such as oxidative coupling reactions other than (1) to (6) are mentioned. By such an oxidation reaction, the oxidizable functional group is oxidized, and an oxidized organic compound is produced.

The metal compound of the present invention is a compound having a novel structure comprising the above-described structure and comprising a structure part derived from a defect structure part-containing heteropolyoxometalate compound and a metal atom different from a heteroatom and a polyatom. Therefore, it is expected to be used in various fields where magnetic materials are used and as a catalyst.

1 is a diagram showing a crystal structure of tetranuclear zinc PW10 synthesized in Example 1. FIG. In FIG. 1, a represents a zinc atom and b represents an oxygen atom. There are four zinc atoms. 3 is a diagram showing a crystal structure of dinuclear cobalt PW10 synthesized in Example 2. FIG. In FIG. 2, b represents an oxygen atom, and c represents a cobalt atom. There are two cobalt atoms. 4 is a view showing a crystal structure of tetranuclear silver GeW10 synthesized in Example 3. FIG. In FIG. 3, d represents a silver atom. There are four silver atoms. 6 is a view showing a crystal structure of hexanuclear silver GeW10 synthesized in Example 4. FIG. In FIG. 4, d represents a silver atom. There are six silver atoms. 6 is a view showing a crystal structure of dinuclear cobalt SiW10 synthesized in Example 5. FIG. In FIG. 5, b represents an oxygen atom and c represents a cobalt atom. There are two cobalt atoms. 6 is a view showing a crystal structure of tetranuclear cobalt cubanSiW10 synthesized in Example 6. FIG. In FIG. 6, b represents an oxygen atom, and c represents a cobalt atom. There are four cobalt atoms. 6 is a view showing a crystal structure of Fe1 synthesized in Example 7. FIG. In FIG. 7, e represents an iron atom. There is one iron atom. 6 is a view showing a crystal structure of FeMn4 synthesized in Example 8. FIG. In FIG. 8, a sphere with a pattern e represents an iron atom, and f represents a manganese atom. There are one iron atom and four manganese atoms. 6 is a diagram showing a crystal structure of Mn5 synthesized in Example 9. FIG. In FIG. 9, f represents a manganese atom. There are five manganese atoms. 6 is a view showing a crystal structure of Co1 synthesized in Example 10. FIG. In FIG. 10, c represents a cobalt atom. There is one cobalt atom. 6 is a view showing a crystal structure of CoMn4 synthesized in Example 11. FIG. In FIG. 11, c represents a cobalt atom, and f represents a manganese atom. There are one cobalt atom and four manganese atoms. 6 is a diagram showing a crystal structure of Ni1 synthesized in Example 12. FIG. In FIG. 12, g represents a nickel atom. There is one nickel atom. 6 is a diagram showing a crystal structure of NiMn4 synthesized in Example 13. FIG. In FIG. 13, g represents a nickel atom, and f represents a manganese atom. There are one nickel atom and four manganese atoms. 14 is a view showing a crystal structure of Cu1 synthesized in Example 14. FIG. In FIG. 14, h represents a copper atom. There is one copper atom. 6 is a view showing a crystal structure of CuMn4 synthesized in Example 15. FIG. In FIG. 15, h represents a copper atom, and f represents a manganese atom. There are one copper atom and four manganese atoms. 6 is a diagram showing a crystal structure of Mn1 synthesized in Example 16. FIG. In FIG. 16, f represents a manganese atom. There is one manganese atom. 6 is a view showing a crystal structure of MnNi 4 synthesized in Example 17. FIG. In FIG. 17, f represents a manganese atom, and a sphere with a g pattern represents a nickel atom. There are one manganese atom and four nickel atoms. 6 is a diagram showing a crystal structure of Cu5 (OMe) synthesized in Example 19. FIG. In FIG. 18, b represents an oxygen atom, and h represents a copper atom. There are five copper atoms. 6 is a diagram showing a crystal structure of Dy6 synthesized in Example 20. FIG. In FIG. 19, b represents an oxygen atom, i represents a dysprodium atom, and j represents a carbon atom. There are six dysprodium atoms. An oxygen atom including acac origin is directly coordinated to the dysprodium atom. FIG. 6 shows a crystal structure (a) of Dy1 synthesized in Example 21 and a crystal structure (b) of DyEu synthesized in Example 22. From SiW ₁₀ via Dy1 DyLn is a diagram showing the reaction to be synthesized (Ln = Eu, Yb, Lu ) and. It is the figure which showed the CSI-MS measurement result of Dy1 (a), DyEu (b), DyYb (c), and DyLu (d) synthesize | combined in Examples 21-24. It is the figure which showed the FT-IR measurement result of DyEu (a), DyYb (b), and DyLu (c) synthesize | combined in Examples 22-24. It is the figure which showed the magnetic measurement result of Dy1 (a), DyEu (b), DyYb (c), and DyLu (d) synthesize | combined in Examples 21-24. FIG. 6 is a diagram showing the magnetic measurement results of DyEu synthesized in Example 22. 10 is a diagram showing the magnetic measurement results of DyDy synthesized in Synthesis Example 5. FIG. It is the figure which showed the magnetic measurement result of DyLu synthesize | combined in Example 24. It is the figure which showed the magnetic measurement result of DyYb synthesize | combined in Example 23. It is the figure which showed the magnetic measurement result of DyYb synthesize | combined in Example 23. The relaxation time is calculated from the frequency dependence of the χ _{m ″} signals of DyEu, DyDy, and DyLu, and lnτ vs.. It is the figure shown as 1 / T plot.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”. “TBA” is an abbreviation for tetra-n-butylammonium, and “acac” is an abbreviation for acetylacetonate.

For X-ray crystal structure analysis, SHELXH-97 was used.
IR measurement was performed using JASCO FT / IR-460.
¹ H-NMR measurement was performed using JEOL JNM-EX-270 at 270 MHz with tetramethylsilane (TMS) as an internal standard.
Cold spray ionization mass spectrometry was performed using JEOL JMS-T100CS.
The magnetic measurement used Quantum Design MPMS-XL7.

Synthesis Example 1 Synthesis of TBA ₃ H ₄ [PW ₁₀ O ₃₆ ] · 3H ₂ O In an ice bath (0 ° C.), 30 mg (0.093 mmol) of TBABr was added to 8 mL of about 2.6 M nitric acid, and Cs ₇ [ PW ₁₀ O ₃₆ ] .H ₂ O 100 mg (0.029 mmol) was added. The mixture was stirred at the same temperature for 10 minutes, and the resulting precipitate was collected by filtration and washed with 10 mL of water. By drying for 5 minutes, 79 mg (82% yield) of TBA ₃ H ₄ [PW ₁₀ O ₃₆ ] was obtained.
This compound can also be synthesized by the following alternative method.
Cs ₇ [PW ₁₀ O ₃₆ ] .H ₂ O 2.0 g (0.59 mmol) was added to 1 L of water, and the pH was adjusted to 2.0 with concentrated nitric acid. After stirring for 5 minutes and removing impurities by filtration, 20 g (62 mmol) of TBABr was added and stirred for 5 minutes. The resulting precipitate was collected by filtration, washed with 1 L of water, and dried to obtain 1.5 g (yield 80%) of TBA ₃ H ₄ [PW ₁₀ O ₃₆ ].

Example 1 Synthesis of Tetranuclear Zinc PW10 94 mg (0.029 mmol) of TBA ₃ [PW ₁₀ O ₃₆ ] was dissolved in 1.5 mL of acetone, and 15 mg (0.058 mmol) of Zn (acac) ₂ was added and stirred. The solution was filtered and allowed to stand to obtain colorless and transparent crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The crystallographic data of the crystals obtained (only the anion structure determined) are as shown in Table 1.

(Example 2) Synthesis of dinuclear cobalt PW10 187 mg (0.058 mmol) of TBA ₃ [PW ₁₀ O ₃₆ ] was dissolved in 3 mL of acetone, and 17 mg (0.058 mmol) of Co (NO ₃ ) ₂ was added thereto for about 15 minutes. A green precipitate was obtained by stirring (yield about 10%). Green crystals were obtained from a mixed solvent of acetonitrile and diethyl ether. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The crystallographic data of the crystals obtained (also TBA confirmed) are shown in Table 2.

Example 3 Synthesis of Tetranuclear Silver GeW10 101 mg (0.029 mmol) of TBA ₄ H ₄ [GeW ₁₀ O ₃₆ ] was dissolved in 2 mL of acetone, and 9.7 mg (0.058 mmol) of AgOAc was added and stirred. A white precipitate was obtained. Colorless transparent crystals were obtained from a mixed solvent of nitromethane and diethyl ether. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
Table 3 shows the crystallographic data of the crystals obtained (only the anion structure determined).

Example 4 Synthesis of Hexanuclear Silver GeW10 101 mg (0.029 mmol) of TBA ₄ H ₄ [GeW ₁₀ O ₃₆ ] was dissolved in 2 mL of acetone, 14.1 mg (0.087 mmol) of AgOAc and [GeW ₁₀ O ₃₆ ] was added with 1 equivalent of dimethylphenylsilane and stirred to obtain a yellow precipitate. Yellow transparent crystals were obtained from a mixed solvent of nitromethane and diethyl ether. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The crystallographic data of the obtained crystals (only the anion structure is determined) are as shown in Table 4.

(Synthesis Example 2) Synthesis of TBA-SiW10 Silicon center two-deficient Keggin type polyoxometalate TBA ₄ H ₄ [γ-SiW ₁₀ O ₃₆ ] · 2H ₂ O (also referred to as “TBA-SiW10”) is as follows. It was synthesized according to the literature.
K. Kamata, K .; Yonehara, Y. et al. Sumida, K .; Yamaguchi, S .; Hikichi, N .; Mizuno, “Science” (USA), 2003, 300, p. 964.

Example 5 Synthesis of Binuclear Cobalt SiW10 (TBA ₆ [Co ₂ {γ-H ₃ SiW ₁₀ O ₃₆ } ₂ ] · 3H ₂ O) To 3 mL of an acetone solution of 200 mg (0.058 mmol) of TBA-SiW10, 17 mg (0.058 mmol) of cobalt nitrate was added, and the resulting yellow precipitate was recovered (yield 69%). Yellow crystals were obtained from a mixed solvent of nitromethane and diethyl ether. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The crystallographic data of the obtained crystals are as shown in Table 5.

(Synthesis Example 3) Tetranuclear cobalt SiW10 (TBA ₆ [{Co (H ₂ O)} ₂ (μ ₃ —OH) ₂ {Co (H ₂ O) ₂ } ₂ {γ-H ₂ SiW ₁₀ O ₃₆ } ₂ 5H ₂ O) (Co4) Synthesis To 1.5 mL of 100 mg (0.029 mmol) of TBA-SiW10 in acetone, 0.017 g (0.058 mmol) of Co (acac) ₂ and 21.2 mg of DMF (0.29 mmol) and 29 μL (0.029 mmol) of 1M nitric acid were added, and the resulting purple precipitate was recovered (yield 80%). Single crystals were obtained by allowing the solution to stand at 30 ° C.

(Example 6) Synthesis of tetranuclear cobalt cubanSiW10 (TBA ₈ [{Co ₂ (OH) ₂ } ₂ {γ-H ₂ SiW ₁₀ O ₃₆ } ₂ ]) 99 mg (0. 0145 mmol) suspended in acetone, 0.029 mL of TBAOH (1M methanol solution) was added, and the mixture was stirred at about 35 ° C. for about 30 minutes, and the precipitated brown powder was recovered (yield about 50%). It was dissolved in a mixed solvent of nitromethane and diethyl ether, allowed to stand once at -20 ° C, and then allowed to stand at 30 ° C to obtain brown crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The crystallographic data of the obtained crystals are as shown in Table 6.

(Synthesis Example 4) Synthesis of SiW9 Silicon center three-deficient Keggin type polyoxometalate SiW9 was synthesized with reference to the following documents.
A. Tze, G.M. Herve, “Inorg. Synth.” (USA), 1990, 27, p. 87.

Example 7 Synthesis of TBA ₇ [Fe (A-α-SiW ₉ O ₃₁ (H ₂ O) ₂ (OH)) ₂ ] · 3H ₂ O (Fe 1) Fe (acac) ₃ was added to a 6 mL screw tube with 52 .4 mg (0.154 mmol) was taken, and 45 mL of acetone and 1.35 mL of water were added. Thereto was added 1.00 g (0.307 mmol) of SiW9 while stirring. After stirring at room temperature for 4 hours, the solution was filtered. 35 mL of diethyl ether was added to the filtrate, and the mixture was allowed to stand overnight to obtain 278 mg (yield 29%) of yellow plate needle-like crystals. The crystallographic data of the obtained crystals are shown in Table 7, and the results of crystal structure analysis are shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement and elemental analysis of the obtained crystals are as follows.
CSI-MS (acetone): m / z [TBA ₉ H ₆ Fe (SiW ₉ O ₃₃ ) ₂ ] ²⁺ 3333 (calculated value), 3333 (measured value); [TBA ₈ H ₆ Fe (SiW ₉ O ₃₃ ) ₂ ] ⁺ : 6423 (calculated value), 6423 (measured value)
Elemental analysis (%) TBA ₇ [Fe (SiW ₉ O ₃₁ (H ₂ O) ₂ (OH))) ₂ ] · 3H ₂ O:
C, 21.45; H, 4.31; N, 1.56; Si, 0.90; W, 52.77; Fe, 0.89 (calculated value)
C, 21.38; H, 4.44; N, 1.58; Si, 0.88; W, 51.1; Fe, 0.87 (measured value)

Example 8 Synthesis of TBA ₇ [FeMn ₄ (OH) ₂ (A-α-SiW ₉ O ₃₄ ) ₂ ] · 2H ₂ O (FeMn4) 120 mg of Fe1 synthesized in Example 7 in a 6 mL screw tube (19 0.1 μmol) and 35 mL of acetone was added. Thereto, 27.0 mg (76.8 μmol) of Mn (acac) ₃ was added with stirring. After stirring at room temperature for 4 hours, diethyl ether was added to obtain 120 mg of a purple powder (yield 97%). 15 mg of the obtained purple powder was dissolved in 20 mL of 1,2-dichloroethane. 0.6 mL of diethyl ether was added and the mixture was allowed to stand overnight to obtain dark brown plate needle crystals. The crystallographic data of the obtained crystals are shown in Table 7, and the results of crystal structure analysis are shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement and elemental analysis of the obtained crystals are as follows.
CSI-MS (1,2-dichloroethane): m / z [TBA ₉ H ₂ FeMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ 3472 (calculated value), 3472 (measured value); [TBA ₈ H ₂ FeMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ⁺ 6703 (calculated value), 6703 (measured value)
Elemental analysis (%) TBA ₇ [FeMn ₄ (OH) ₂ (SiW ₉ O ₃₄ ) ₂ ] · 5H ₂ O:
C, 20.71; H, 4.00; N, 1.51; Si, 0.86; W, 50.94; Fe, 0.86; Mn, 3.38 (calculated value)
C, 20.65; H, 3.93; N, 1.40; Si, 0.79; W, 51.1; Fe, 1.02; Mn, 3.59 (measured value)

Example 9 Synthesis of TBA ₇ [Mn ₅ (OH) ₂ (A-α-SiW ₉ O ₃₄ ) ₂ ] · 2H ₂ O · CH ₂ ClCH ₂ Cl (Mn5) Mn (acac) _{3 in a} 6 mL screw tube 27.1 mg (77.3 μmol) was taken, and 10 mL of acetone was added. Thereto, 100 mg (30.9 μmol) of SiW9 was added while stirring. After stirring at room temperature for 2 hours, the solution was filtered. Diethyl ether was added to the filtrate to obtain 87.6 mg of a brown powder (yield 88%). 10 mg of the obtained brown powder was dissolved in 10 mL of 1,2-dichloroethane, and then 0.8 mL of ethyl acetate was added. By standing overnight at 293K, 4.3 mg (43% yield) of dark brown block crystals were obtained. The crystallographic data of the obtained crystals are shown in Table 7, and the results of crystal structure analysis are shown in FIG.
The results of FT-IR, cold spray ionization mass spectrometry (CSI-MS) measurement, and elemental analysis of the obtained crystal are as follows.
FT-IR (KBr): 1700, 1380, 1153, 1107, 1014, 990, 957, 934, 923, 709, 669, 614, 534, 480, 410, 376, 344, 333, 262, 255, 269 cm ¹
CSI-MS (1,2-dichloroethane): m / z [TBA ₉ H ₂ Mn ₅ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ 3472 (calculated value), 3472 (measured value); [TBA ₈ H ₂ Mn ₅ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ⁺ 6702 (calculated value), 6702 (measured value)
Elemental analysis (%) TBA ₇ [Mn ₅ (OH) ₂ (SiW ₉ O ₃₄ ) ₂ ] · 2H ₂ O · CH ₂ ClCH ₂ Cl:
C, 20.7; H, 4.00; N, 1.49; Si, 0.85; W, 50.2; Mn, 4.17 (calculated value)
C, 20.3; H, 3.93; N, 1.20; Si, 0.89; W, 50.0; Mn, 4.48 (measured value)

Example 10 Synthesis of TBA ₇ H ₁₁ [Co (A-α-SiW ₉ O ₃₄ ) ₂ ] · 3H ₂ O (Co1) 4.50 mg Co (acac) ₃ · 2H ₂ O in a 6 mL screw tube 0.0154 mmol), and 2.85 mL of acetone and 0.15 mL of water were added. Thereto, 100 mg (0.0307 mmol) of SiW9 was added with stirring. After stirring at room temperature for 4 hours, the solution was filtered. 10 mL of diethyl ether was added to the filtrate to obtain 69 mg (yield 72%) of pink powder. This powder was recrystallized in dichloroethane / diethyl ether to obtain orange crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The measurement results of FT-IR and cold spray ionization mass spectrometry (CSI-MS) of the obtained crystals are as follows.
FT-IR (KBr): 1630, 1484, 1380, 1152, 1006, 957, 919, 875, 789, 534, 429, 378, 361, 313, 301, 293, 287, 271, 263, 252 cm ¹
CSI-MS (acetone): m / z [TBA ₉ CoOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 3307 (calculated value), 3307 (measured value); [TBA ₈ CoOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 6372 (calculated value), 6372 (measured value)

(Example 11) Synthesis of TBA ₇ H [CoMn ₄ (OH) ₂ (A-α-SiW ₉ O ₃₄ ) ₂ ] · 2H ₂ O (CoMn 4) 44. 0 mg (7.01 μmol) was taken and 4 mL of dichloroethane was added. 9.88 mg (28.0 μmol) of Mn (acac) ₃ was added thereto with stirring. After stirring at room temperature for 4 hours, diethyl ether was added to the solution to obtain 39 mg (yield 86%) of a purple powder. 38 mg of this powder was dissolved in 3 mL of 1,2-dichloroethane, and 1.5 mL of diethyl ether was added. A dark brown plate needle crystal was obtained by allowing to stand overnight. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement of the obtained crystals are as follows.
CSI-MS (1,2-dichloroethane): m / z [TBA ₉ H ₃ CoMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ : 3475 (calculated value), 3475 (measured value); [TBA ₈ H ₃ CoMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ⁺ : 6706 (calculated value), 6706 (measured value)

(Example _{12) TBA 7 H 11 [Ni} (A-α-SiW 9 O 34) 2] · 3H 2 O (Ni1) Synthesis 6mL screw tube in _{Ni (acac) 3 · 2H 2} O to 4.49Mg ( 0.0154 mmol), and 2.85 mL of acetone and 0.15 mL of water were added. Thereto, 100 mg (0.0307 mmol) of SiW9 was added with stirring. After stirring at room temperature for 4 hours, the solution was filtered. 10 mL of diethyl ether was added to the filtrate to obtain 76 mg (yield 79%) of white powder. This powder was recrystallized in dichloroethane / diethyl ether to obtain greenish white crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The measurement results of FT-IR and cold spray ionization mass spectrometry (CSI-MS) of the obtained crystals are as follows.
FT-IR (KBr): 296, 1933, 2872, 1632, 1485, 1380, 1153, 1107, 994, 953, 903, 816, 797, 768, 729, 559, 523, 455, 361, 336cm ¹
CSI-MS (acetone): m / z [TBA ₉ NiOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 3307 (calculated value), 3307 (measured value); [TBA ₈ NiOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 6372 (calculated value), 6372 (measured value)

(Example 13) Synthesis of TBA ₇ H [NiMn ₄ (OH) ₂ (A-α-SiW ₉ O ₃₄ ) ₂ ] · 2H ₂ O (NiMn4) Ni1 synthesized in Example 12 in a 6 mL screw tube was obtained in 41. 0 mg (6.53 μmol) was taken and 4 mL of dichloroethane was added. Thereto was added 9.20 mg (26.1 μmol) of Mn (acac) ₃ with stirring, followed by stirring at room temperature for 4 hours. Thereafter, diethyl ether was added to the solution to obtain 39 mg (yield 86%) of a purple powder. 38 mg of this powder was dissolved in 3 mL of 1,2-dichloroethane, and 1.5 mL of diethyl ether was added. A dark brown plate needle crystal was obtained by allowing to stand overnight. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement of the obtained crystals are as follows.
CSI-MS (1,2-dichloroethane): m / z [TBA ₉ H ₃ NiMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ : 3475 (calculated value), 3475 (measured value); [TBA ₈ H ₃ NiMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ⁺ : 6706 (calculated value), 6706 (measured value)

Example 14 Synthesis of TBA ₇ H ₁₁ [Cu (A-α-SiW ₉ O ₃₄ ) ₂ ] · 3H ₂ O (Cu1) 9.19 mg Cu (acac) ₂ · H ₂ O in a 6 mL screw tube 0.0461 mmol), and 9.5 mL of acetone and 0.5 mL of water were added. Thereto, 300 mg (0.0921 mmol) of SiW9 was added with stirring. After stirring at room temperature for 3 hours, the solution was filtered. 10 mL of diethyl ether was added to the filtrate to obtain 277 mg (yield 96%) of white powder. This powder was recrystallized in dichloroethane / diethyl ether to obtain greenish white crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement of the obtained crystals are as follows.
CSI-MS (acetone): m / z [TBA ₉ CuOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 3310 (calculated value), 3310 (measured value); [TBA ₈ CuOH (SiW ₉ O ₃₁ ) ₂ ] ²⁺ : 6377 (calculated value), 6377 (measured value)

(Example _{15) TBA 7 H [CuMn 4} (OH) 2 (A-α-SiW 9 O 34) 2] · 2H 2 O (CuMn4) Synthesis 6 mL Cu1 50 synthesized screw tube in Example 14. 0 mg (7.96 μmol) was taken and 4 mL of dichloroethane was added. Thereto was added 11.2 mg (31.8 μmol) of Mn (acac) ₃ with stirring, followed by stirring at room temperature for 4 hours. Thereafter, diethyl ether was added to the solution to obtain 40 mg (yield 86%) of a purple powder. 30 mg of this powder was dissolved in 3 mL of 1,2-dichloroethane, and 1.7 mL of diethyl ether was added. A dark brown plate needle crystal was obtained by allowing to stand overnight. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement of the obtained crystals are as follows.
CSI-MS (1,2-dichloroethane): m / z [TBA ₉ H ₃ CuMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ : 3477 (calculated value), 3477 (measured value); [TBA ₈ H ₃ CuMn ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ⁺ : 6711 (calculated value), 6711 (measured value)

Example 16 Synthesis of TBA ₇ [Mn (A-α-SiW ₉ O ₃₁ (H ₂ O) ₂ (OH)) ₂ ] · 3H ₂ O (Mn 1) 5 Mn (acac) ₃ was added to a 6 mL screw tube. .42 mg (15.5 μmol) was taken, and 10 mL of acetone was added. Thereto, 100 mg (30.9 mol) of SiW9 was added with stirring. After stirring at room temperature for 2 hours, the solution was filtered. Diethyl ether (0.5 mL) was added to the filtrate, and the mixture was allowed to stand at 293 K overnight to obtain 53.3 mg (yield 55%) of yellow plate needle-like crystals. The crystallographic data of the obtained crystals are shown in Table 8, and the results of crystal structure analysis are shown in FIG.
The results of FT-IR, cold spray ionization mass spectrometry (CSI-MS) measurement, and elemental analysis of the obtained crystal are as follows.
FT-IR (KBr): 1630, 1484, 1380, 1152, 1006, 957, 919, 875, 789, 534, 429, 378, 361, 313, 301, 293, 287, 271, 263, 252 cm ¹
CSI-MS (acetone): m / z [TBA ₉ H ₆ Mn (SiW ₉ O ₃₃ ) ₂ ] ²⁺ : 3332 (calculated value), 3332 (measured value); [TBA ₈ H ₆ Mn (SiW ₉ O ₃₃ ) ₂ ] ⁺ : 6422 (calculated value), 6422 (measured value)
Elemental analysis (%) TBA ₇ [Mn (SiW ₉ O ₃₁ (H ₂ O) ₂ (OH)) ₂ ] · 3H ₂ O:
C, 21.5; H, 4.33; N, 1.56; Si, 0.90; W, 52.8; Mn, 0.88 (calculated value)
C, 21.3; H, 4.25; N, 1.40; Si, 0.88; W, 51.1; Mn, 0.87 (measured value)

Example 17 Synthesis of TBA ₇ [MnNi ₄ (OH) ₂ (A-α-SiW ₉ O ₃₄ ) ₂ ] · 5H ₂ O (MnNi 4) 10 mg of Mn1 synthesized in Example 16 in a 6 mL screw tube (1 .60 μmol) and 10 mL of acetone was added. Thereto, 1.59 mg (6.39 μmol) of Ni (OAc) ₂ was added while stirring. After stirring at room temperature for 5 hours, the solution was filtered. 4 mL of diethyl ether was added to the filtrate, and the mixture was allowed to stand at 293 K overnight to obtain 1.8 mg (yield 17%) of light brown plate crystals. The crystallographic data of the obtained crystals are shown in Table 8, and the results of crystal structure analysis are shown in FIG.
The results of FT-IR, cold spray ionization mass spectrometry (CSI-MS) measurement, and elemental analysis of the obtained crystal are as follows.
FT-IR (KBr): 1631, 1484, 1382, 1152, 997, 954, 908, 809, 775, 634, 538, 373, 332, 317, 257, 253 cm ¹
CSI-MS (acetonitrile): m / z [TBA ₉ H ₆ MnNi ₄ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ 3466 (calculated value), 3466 (measured value); [TBA ₈ H ₆ MnNi ₄ O ₂ ( SiW ₉ O ₃₄ ) ₂ ] ⁺ 6688 (calculated value), 6688 (measured value)
Elemental analysis (%) TBA ₆ H ₈ [Cu ₅ O ₂ (SiW ₉ O ₃₄ ) ₂ ] · 5H ₂ O:
C, 20.6; H, 4.13; N, 1.50; Si, 0.86; W, 50.6; Mn, 0.84; Ni, 3.59 (calculated value)
C, 21.9; H, 4.15; N, 1.55; Si, 0.79; W, 51.1; Mn, 1.02; Ni, 3.59 (measured value)

Example 18 Synthesis of TBA ₇ H ₂ [Cu ₅ (A-α-SiW ₉ O ₃₄ ) ₂ ] · CH ₃ COCH ₃ · 2H ₂ O (Cu5) 10 mg (3.08 μmol) of SiW9 in a 6 mL screw tube And 1 mL of acetone and 0.1 mL of H ₂ O were added. While stirring, 1.53 mg (7.73 μmol) of Cu (OAc) ₂ was added. After stirring at room temperature for 2 hours, the solution was filtered. 2.9 mL of ethyl acetate was added to the filtrate. By standing overnight at 293 K, 5.8 mg (yield 60%) of green plate crystals were obtained.
The results of FT-IR, ¹ H-NMR, cold spray ionization mass spectrometry (CSI-MS) measurement and elemental analysis of the obtained crystals are as follows.
FT-IR (KBr): 1484, 1466, 996, 963, 910, 779, 693, 548, 379, 345, 256 cm ^1
1 H-NMR (270.05 MHz, DMSO-d ₆ , 298 K, TMS): δ = 0.94 (t, J ₂ = 8.12 Hz, 96H), 1.26-1.37 (m, 64H), 1.57 (m, 64H), 2.10 (s, 6H, acetone), 3.15-3.23 ppm (m, 64H)
CSI-MS (acetonitrile): m / z [TBA ₈ H ₈ Cu ₅ O ₂ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ 3375 (calculated value), 3375 (measured value); [TBA ₇ H ₈ Cu ₅ O ₂ ( SiW ₉ O ₃₄ ) ₂ ] ⁺ 6508 (calculated value), 6508 (measured value)
Elemental analysis _{(%) TBA 6 H 8 [} Cu 5 O 2 (SiW 9 O 34) 2] · CH 3 COCH 3 · 2H 2 O:
C, 18.7; H, 3.71; N, 1.32; Si, 0.88; W, 52.0; Cu, 5.00 (calculated value)
C, 18.7; H, 3.86; N, 1.30; Si, 0.82; W, 51.3; Cu, 4.88 (measured value)

Example 19 Synthesis of TBA ₄ [Cu ₅ (A-α-SiW ₉ O ₃₀ ) ₂ (OCH ₃ ) ₁₀ ] (Cu5 (OMe)) Take 10 mg (3.08 μmol) of SiW9 in a 6 mL screw tube, and add methanol. After adding 6 mL, the mixture was stirred for 1 hour. Thereto, 1.53 mg (7.73 μmol) of Cu (OAc) ₂ was added while stirring. After stirring at room temperature for 1 hour, the solution was filtered. The filtrate was allowed to stand at 293 K overnight to obtain 2.0 mg (yield 22%) of green hexagonal columnar crystals. The crystallographic data of the obtained crystals are shown in Table 8, and the results of crystal structure analysis are shown in FIG.
The measurement results of FT-IR of the obtained crystals are as follows.
FT-IR (KBr): 1630, 1484, 1466, 1383, 996, 963, 910, 779, 693, 548, 379, 345, 256 cm ¹

(Example 20) Synthesis of TBA ₇ H [Dy ₆ (A-α-SiW ₉ O ₃₄ ) ₂ (acac) ₃ (H ₂ O) ₃ (OH) ₃ ] (Dy6) 50 mg of SiW9 in a 6 mL screw tube ( 15.4 μmol) and 1 mL of acetone and 0.1 mL of H ₂ O were added. 22.8 mg (46.0 μmol) of Dy (acac) ₃ .2H ₂ O was added thereto while stirring. After stirring at room temperature for 1 hour, the solution was filtered. 5.7 mL of diethyl ether was added to the filtrate, and the mixture was allowed to stand overnight to obtain 31 mg (yield 54%) of colorless plate crystals. The result of the crystal structure analysis of the obtained crystal is shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement of the obtained crystals are as follows.
CSI-MS (acetonitrile): m / z [TBA ₉ HDy ₆ (C ₅ H ₇ O ₂ ) ₃ (OH) ₃ (SiW ₉ O ₃₄ ) ₂ ] ²⁺ 3980 (calculated value), 3980 (measured value); TBA ₈ HDy ₆ (C ₅ H ₇ O ₂ ) ₃ (OH) ₃ (SiW ₉ O ₃₄ ) ₂ ] ⁺ 7714 (calculated value), 7714 (measured value)

Example 21 Synthesis of TBA ₈ H ₅ [{Dy (H ₂ O) ₄ } (γ-SiW ₁₀ O ₃₆ ) ₂ ] (Dy1) In a mixed solvent of acetone and water (20 / 0.3 mL), TPA- the SiW10 1.00g (0.291mmol), Dy ( acac) 3 · 2H 2 O and 66.9 mg (0.146 mmol, 0.5 equivalents relative _{SiW 10)} was added, 90 minutes at room temperature (about 20 ° C.) Stir. Then, 5 mL of diethyl ether was added, and the solution was allowed to stand at 25 ° C. for 1 day to obtain 661 mg (yield 63% with respect to SiW ₁₀ ) of colorless crystals. The crystallographic data of the obtained crystals are shown in Table 9, and the results of crystal structure analysis are shown in FIG.
The results of cold spray ionization mass spectrometry (CSI-MS) measurement and elemental analysis of the obtained crystals are as follows. The measurement spectrum of CSI-MS is shown in FIG. Insets in FIG. 22 (a) are m / z 3720-3760, measured values in the range 7200-7260, and [TBA ₁₀ H ₅ Dy (SiW ₁₀ O ₃₆ ) ₂ ] ²⁺ (m / z 3739). And [TBA ₉ H ₅ Dy (SiW ₁₀ O ₃₆ ) ₂ ] ⁺ (m / z 7235).
CSI-MS (acetonitrile): m / z [TBA ₁₀ H ₅ Dy (SiW ₁₀ O ₃₆ ) ₂ ] ²⁺ 3738 (calculated value), 3738 (measured value); [TBA ₁₀ H ₅ Dy (H ₂ O) (SiW ₁₀ O ₃₆ ) ₂ ] ²⁺ 3747 (calculated value), 3747 (measured value)
Elemental analysis (%) TBA ₈ H ₅ [Dy (H ₂ O) ₄ (SiW ₁₀ O ₃₆ ) ₂ ] .6H ₂ O. (CH ₃ COCH ₃ ):
C, 21.76; H, 4.45; N, 1.55; Si, 0.78; W, 50.85; Dy, 2.25 (calculated value)
C, 21.73; H, 4.29; N, 1.61; Si, 0.76; W, 50.15; Dy, 2.14 (measured value)

(Synthesis Example 5) Synthesis of TBA ₈ [DyDy (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] (DyDy) DyDy was synthesized according to the following literature.
K. Suzuki, R.A. Sato, N .; Mizuno, “Chem. Sci.” (UK), 2013, Vol. 4, p. 596.

Example 22 Synthesis of TBA ₈ [DyEu (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] (DyEu) 180 mg (0.025 mmol) of Dy1 synthesized in Example 5 in 2 mL of 1,2-dichloroethane , 15 mg (0.031 mmol, 1.25 equivalents to Dy1) of Eu (acac) ₃ .H ₂ O was added, and the mixture was stirred at room temperature (about 20 ° C.) for 30 minutes. Thereafter, 5 mL of diethyl ether was added. The produced white precipitate (168 mg) was taken out by filtration and recrystallized with dehydrated dichloromethane in the presence of molecular sieve 3A to obtain 23 mg (yield 13% with respect to Dy1) of colorless crystals. The crystallographic data of the obtained crystals are shown in Table 9, and the results of crystal structure analysis are shown in Table 10 and FIG. 20 (b). FIG. 21 shows the reaction until DyLn (Ln = Eu, Yb, Lu) is synthesized from SiW ₁₀ via Dy1.
The results of cold spray ionization mass spectrometry (CSI-MS), FT-IR measurement, and elemental analysis of the obtained crystals are as follows. The measurement spectrum of CSI-MS is shown in FIG. The inset in FIG. 22 (b) shows the measured values in the range of m / z 7380-7460 and [TBA ₉ DyEu (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ (m / z 7420). This is a simulated pattern. Moreover, the measurement result of FT-IR was shown to Fig.23 (a).
CSI-MS (acetonitrile): m / z [TBA ₉ DyEu (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ 7420 (calculated value), 7420 (measured value); [TBA ₁₀ DyEu (OH) ₂ ( H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ²⁺ 3831 (calculated value), 3831 (measured value)
FT-IR (KBr): 3646, 2961, 2931, 2873, 1635, 1483, 1380, 1153, 1103, 1000, 955, 868, 758, 559 cm ¹
Elemental analysis (%) TBA ₈ [DyEu (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] .H ₂ O:
H, 4.15; N, 1.56; Si, 0.78; W, 51.10; Dy, 2.26; Eu, 2.11 (calculated value)
C, 21.18; H, 4.07; N, 1.45; Si, 0.73; W, 47.98; Dy, 2.28; Eu, 2.39 (measured value)

Example 23 Synthesis of TBA ₈ [DyYb (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] (DyYb) Instead of using Eu (acac) ₃ .H ₂ O, Yb (acac) ₃ .2H ₂ O Was used in the same manner as in Example 22 except that 1.25 equivalent was used relative to Dy1, and colorless crystals (yield 14% based on Dy1) were obtained. The crystallographic data of the obtained crystals are shown in Table 9, and the results of crystal structure analysis are shown in Table 10.
The results of cold spray ionization mass spectrometry (CSI-MS), FT-IR measurement, and elemental analysis of the obtained crystals are as follows. The measurement spectrum of CSI-MS is shown in FIG. The inset in FIG. 22 (c) shows measured values in the range of m / z 7400-7480 and [TBA ₉ DyYb (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ (m / z 7441). This is a simulated pattern. Moreover, the measurement result of FT-IR was shown in FIG.23 (b).
CSI-MS (acetonitrile): m / z [TBA ₉ DyYb (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ 7441 (calculated value), 7441 (measured value); [TBA ₁₀ DyYb (OH) ₂ ( H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ²⁺ 3842 (calculated value), 3842 (measured value)
FT-IR (KBr): 3649, 2960, 2873, 1635, 1483, 1380, 1153, 1097, 998, 953, 890, 868, 763, 557 cm ¹
Elemental analysis (%) TBA ₈ [DyYb (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] · 6H ₂ O:
C, 21.04; H, 4.22; N, 1.56; Si, 0.77; W, 50.32; Dy, 2.22; Yb, 2.37 (calculated value)
H, 4.24; N, 1.44; Si, 0.70; W, 48.70; Dy, 2.21; Eu, 2.36 (measured value)

(Example _{24) TBA 8 [DyLu (OH} ) 2 (H 2 SiW 10 O 36) 2] (DyLu) Synthesis _{Eu (acac) 3 · H 2} O Instead of using _{Lu (acac) 3 · 2H 2} O Was used in the same manner as in Example 22 except that 1.25 equivalents were used with respect to Dy1, and colorless crystals (yield 51% with respect to Dy1) were obtained. The crystallographic data of the obtained crystals are shown in Table 9, and the results of crystal structure analysis are shown in Table 10.
The measurement results of cold spray ionization mass spectrometry (CSI-MS) and FT-IR of the obtained crystals are as follows. The measured spectrum of CSI-MS is shown in FIG. The inset in FIG. 22D is an actual measurement value in the range of m / z 7400-7480 and a simulated pattern of [TBA ₉ DyLu (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ (m / z 7442). is there. Moreover, the measurement result of FT-IR was shown in FIG.23 (c).
CSI-MS (acetonitrile): m / z [TBA ₉ DyLu (OH) ₂ (H ₂ SiW ₁₀ O ₃₆ ) ₂ ] ⁺ 7443 (calculated value), 7443 (measured value); [TBA ₁₀ DyLu (OH) ₂ ( _{H 2 SiW 10 O 36) 2} ] 2+ 3843 ( calc) 3843 (measured value)
FT-IR (KBr): 3647, 2961, 2934, 2873, 1635, 1483, 1380, 1153, 1095, 999, 954, 889, 868, 761, 556 cm ¹

(Magnetic measurement)
Magnetic measurements were performed on each metal compound obtained in the examples. The results are shown in FIGS.
From the dc magnetic measurement at 1000 Oe, χ _m T (300 K) of DyEu, DyYb, and DyLu were 15.3, 16.2, and 14.1 cm ³ Kmol ⁻¹ , respectively. The χmT of DyLu is the same as the value of Dy1, the values of DyEu and DyYb are larger than the value of Dy1, and the magnetic susceptibility of DyEu (Eu ³⁺ cation is the initial low-lying state with energy of 0, λ, 3λ. It was in agreement with the theoretical value of DyYb) (calculated from the Van Vlek equation when allowed). Next, AC magnetic susceptibility measurement in a zero magnetic field of DyEu, DyYb, DyLu, and DyDy was performed. In DyEu and DyLu, signals of χ _m ′ and χ _m ″ derived from Dy ³⁺ depending on the temperature and magnetic field, which are characteristic of the behavior of a single molecule magnet, were observed. For DyYb, only a small signal was observed in a zero magnetic field. This is probably due to strong quantum tunneling (QTM) with Yb ³⁺ adjacent to Dy ³⁺ . Under an external magnetic field of 1800 Oe, QTM is suppressed, and DyYb also shows χ _m ′ and χ _{m ″} signals that are significantly dependent on temperature and magnetic field, and DyYb exhibits single-molecule magnet behavior under an external magnetic field. Was suggested. It was suggested that DyDy also exhibits a single molecule magnet behavior.
The relaxation time is calculated from the frequency dependence of the χ _{m ″} signals of DyEu, DyDy, and DyLu, and lnτ vs.. Shown as 1 / T plot (FIG. 30). This plot was fitted according to Arrhenius law, and the magnetization reversal energy barrier (ΔE / kB) and pre-exponential factor, 73.0K, and 1.8 × 10 ⁻⁷ s (DyEu), 65.7K, and 3 Obtained 1 × 10 ⁻⁷ s (DyDy), 46.7K, and 1.9 × 10 ⁻⁶ s (DyLu). The energy barrier is DyLu (46.7K) <DyDy
Increasing in the order (65.7K) <DyEu (73.0K), DyEu showed the highest energy barrier of these structures. The order of the energy barriers was in good agreement with the order of the ionic radius 12 of the lanthanoid cations adjacent to Dy ³⁺ . This is because the {Dy (μ2-OH) 2Ln} core having a larger Ln ³⁺ cation has a small interaction between the 4f electron density of Dy ³⁺ and the oxygen atom of the ligand, resulting in a large anisotropy. It is thought that this is because it was obtained. There has never been an example in which the activation barrier of single-molecule magnet behavior is controlled by heteronucleation of lanthanoid metals. DyEu has the highest energy barrier among single-molecule magnets using polyoxometalate ligands.

a: zinc atom b: oxygen atom c: cobalt atom d: silver atom e: iron atom f: manganese atom g: nickel atom h: copper atom i: dysprodium atom j: carbon atom

Claims (5)

A metal compound having two or more structural sites derived from a deficient structural site-containing heteropolyoxometalate compound,
The heteropolyoxometalate compound has a structure in which a poly atom is coordinated to an hetero atom via an oxygen atom,
The metal compound has a structural moiety derived from two defective structure site and / or three defective structure unit position containing organic hetero polyoxometalate compound, it contains different metal atoms with heteroatoms and poly atom,
The two- deficient structure site-containing heteropolyoxometalate compound contains at least one heteroatom selected from the group consisting of P, Si and Ge ,
The three-deficient structure site-containing heteropolyoxometalate compound contains at least one heteroatom selected from the group consisting of P, Si and Ge, and the polyatom is W;
The metal atom is Ag, the heteroatom is Ge, and at least one of the metal atoms is only one polyatom per structural site derived from one heteropolyoxometalate compound and one oxygen atom A structure in which any of the metal atoms is coordinated and the metal atoms are coordinated via one oxygen atom,
The metal atom is at least one atom selected from the group consisting of Dy, Eu, Yb, Lu, Mn, Fe, Co, Ni, Cu, and Ag, and at least one of the metal atoms is two Coordination via a poly atom and one oxygen atom in the structural site derived from the above heteropolyoxometalate compound, and two or more polyatoms and one per structural site derived from one heteropolyoxometalate compound A structure coordinated through an oxygen atom (provided that when the metal atom is Ag, the heteroatom is Ge),
A structure in which the metal atom is Ag, a heteroatom is Ge, and the four metal atoms are directly bonded to each other with at least two other metal atoms; and
A structure in which the metal atom is Co and the four metal atoms are coordinated to the other three metal atoms through one oxygen atom.
A metal compound having at least one structure selected from: The metal compound has a structural site derived from a two-deficient structural site-containing heteropolyoxometalate compound,
The two-deficient structure site-containing heteropolyoxometalate compound contains at least one heteroatom selected from the group consisting of P, Si and Ge,
The metal compound according to claim 1, wherein the metal atom is at least one atom selected from the group consisting of Dy, Eu, Yb, Lu, Co, and Ag . The metal compound has a structural site derived from a three-deficient structural site-containing heteropolyoxometalate compound,
The three-deficient structure site-containing heteropolyoxometalate compound contains a Si heteroatom,
The metal compound according to claim 1, wherein the metal atom is at least one atom selected from the group consisting of Dy, Mn , Fe, Co, Ni, and Cu . The metal compound according to claim 1, wherein the defect structure site-containing heteropolyoxometalate compound is a Keggin type heteropolyoxometalate compound. The metal compound according to any one of claims 1 to 4, wherein the defect structure site-containing heteropolyoxometalate compound is at least one selected from the group consisting of α-form, β-form and γ-form. .