WO2022014702A1 - Metal-organic framework, and method for manufacturing same - Google Patents

Abstract

Provided are a metal-organic framework suitably used as a functional material, and a method for manufacturing same, the metal-organic framework containing a cluster (α) and a cluster (β) as constituent units respectively, wherein the cluster (α) contains a metal ion (Mα ion) and ligands (ligands Lα) that coordinate with the Mα ion, the cluster (β) contains a cubane-type structure containing a metal ion (Mβ ion) as an essential component, and at least one of the ligands Lα is a polydentate ligand (ligand Lα 1) that also coordinates with the Mβ ion.

Description

Metal-organic framework and its manufacturing method

The present invention relates to a metal-organic framework and a method for producing the same.

The metal organic structure (MOF) is a compound having a coordination network structure constructed by a coordinate bond between a metal ion and a polydentate ligand and a covalent bond in the polydentate ligand. Since some metal-organic frameworks have relatively large voids inside, such metal-organic frameworks are expected as functional porous materials such as gas adsorbents, gas storage materials, and gas separators. ..

In recent years, the selectivity of the uptake of molecules into the voids has been improved, and new functions have been added to the molecular chains constituting the coordination network structure (hereinafter, sometimes referred to as "metal-organic polymer chains"). In order to do so, a second metal ion is introduced into the metal-organic polymer chain in addition to the first metal ion for maintaining the coordination network structure.

For example, Non-Patent Document 1 describes [Zn ₂ (bpdc) ₂ L] (bpdc = biphenyldicularboxylate, L = (R, R)-(−) -1,2-cyclohexanediamino-N, N'-bis (3-). tert-butyl-5- (4-pyridyl) catalyst Mn ^III Cl) (metal-organic framework in which an active site having a manganese ion is incorporated in a metal-organic polymer chain) is 2,2-dimethyl-2H-. It has been described that it is useful as a catalyst for the asymmetric epoxidation reaction of chromene.

In connection with the present invention, it is known that a small molecule complex containing a cubane-type structure has interesting properties as a magnetic material.
For example, Non-Patent Document 2, ^{Dy 3+} and (dysprosium ion) OH ^- cubane-type structure to (hydroxo ions) components containing _{([Dy 4 (μ 3 -OH} ) 4] structure), and two The molecular structure of the low molecular weight complexes and the magnetic properties of these low molecular weight complexes are described. In Non-Patent Document 2, although the cubane-type structures of these small molecule complexes are similar, a slight difference in the angle of Dy—O—Dy greatly affects the difference in the magnetic properties of the small molecule complex. Is also described.
Further, conventionally, compounds containing rare earth elements have been used as light emitting materials and the like.

International Publication No. 2018/079831

As described above, the metal-organic framework having a metal-organic polymer chain into which a metal ion having functionality is introduced is extremely useful as a functional material such as a catalyst material, a magnetic material, and a light emitting material.
Further, as described in Non-Patent Document 2, it is important to investigate the relationship between the molecular structure of a functional material and its function and obtain new findings in order to improve the functional material, but it is low. In order to clarify the molecular structure of a molecular complex, a crystallization step for obtaining a sample for single crystal X-ray crystal structure analysis is indispensable in addition to the step of synthesizing the low molecular complex.
On the other hand, in the metal-organic framework, usually, the obtained metal-organic structure can be used as it is as a sample for single crystal X-ray crystal structure analysis, so that the functional material composed of the metal-organic structure can be used. Suitable for further enhancement of functionality.

Under such circumstances, an object of the present invention is to provide a metal-organic framework containing a cubane-type structure, which is suitably used as a functional material, and a method for producing the same.

The present inventors have accumulated anionic polynuclear metal complexes to form a crystal lattice, and an ionic solid formed by the presence of a cationic species in the gaps of the crystal lattice has ionic conduction because the cationic species has high motility. It has been found to be useful as a body (Patent Document 1).
As a result of further studies by the present inventors, the molecular structure of the polynuclear metal complex containing a plurality of metal ions and having an appropriate size, such as this anionic polynuclear metal complex, is a metal containing a Cuban-type structure. We have found that it is also suitable as a partial structure of an organic structure, and have completed the present invention.

Thus, according to the present invention, the following metal-organic frameworks [1] to [14] and a method for producing the metal-organic framework [15] are provided.
[1] A metal-organic framework containing a cluster (α) and a cluster (β) as constituent units, respectively, in which the cluster (α) coordinates with _{a metal ion (M α} ion) and an M _{α ion.} It contains a ligand (ligand L _α ), and the cluster (β) _{contains a Cuban-type structure having a metal ion (M β} ion) as an essential component, and the ligand L _α. at least one is a polydentate ligand coordinating to M _beta ions (ligand L _alpha ^1), metal organic structures.
_{[2] Coordination with a divalent or trivalent metal ion (M α} ¹ ion) in which the cluster (α) can form a complex having an octahedral molecular structure having a coordination number of 6 as _{the M α ion.} capable of forming a complex with a tetrahedral molecular structure of 4, monovalent or divalent metal ion (M _alpha ² ions), is intended to include metal organic structure according to [1].
[3] The M _α ¹ ion is an ion of one kind of metal selected from the group consisting of the metals of the 8th, 9th, and 10th groups of the periodic table, Cr, and Mn, and the M _α ² ion is an ion. The metal organic structure according to [2], which is an ion of one kind of metal selected from the group consisting of the metals of Group 11 and Group 12 of the Periodic Table.
[4] The metal-organic framework according to any one of [1] to [3], wherein the _{ligand Lα} ^{1 is represented by the following formula (1).}

Wherein (1), ^{T 1} represents a first atom (ligand atoms ^{t 1)} or a group containing a coordination atom ^{t 1} coordinating to M _alpha ion, ^{T 2} is coordinated to M _alpha ion Represents a group containing a ^second atom (coordinating atom t ² ) or a coordinating atom t ^{2, where T 3} is an _{atom coordinating to an M β} ion (coordinating atom t ³ ) or a coordinating atom t ³ . Represents a group containing, and G represents a linking group. T ^1- GT ² is an atomic group that forms a 5-membered chelate ring or a 6-membered chelate ring by coordinating the coordination atom t ¹ and the coordination atom t ² to the M _{α ion.}
[5] The metal-organic framework according to any one of [1] to [4], wherein the _{ligand Lα} ^{1 is an amino acid.}
[6] The metal-organic framework according to any one of [1] to [5], wherein the cluster (α) is represented by the following formula (2).

In formula (2), M _α ¹ represents a divalent or trivalent metal ion capable of forming a complex having an octahedral molecular structure having a coordination number of 6, and M _α ² is a tetrahedron having a coordination number of 4. Represents a monovalent or divalent metal ion capable of forming a complex of body type molecular structure, L _α ¹ represents a polydentate ligand that also coordinates with M _β ^{ion, and E represents H −} , O ^{2 -, S 2-, Se 2-,} Te 2-, F -, Cl -, Br - or I ^- it represents a. m is 0 or 1, and n is ( _{valence of M α} ¹ × 4) + ( _{valence of M α} ² × 4) + ( _{valence of L α} ¹ × 12) + (valence of E). It is a number calculated by × m).
[7] The aggregate of clusters (α) is derived from the anion portion of the ionic flow type ionic solid, and the ionic flow type ionic solid contains a metal ion and a polydentate ligand. The metal organic structure according to any one of [1] to [6], wherein the anionic polynuclear metal complex accumulates to form a crystal lattice, and a cationic species exists in the gaps of the crystal lattice.
[8] _{The metal-organic framework according to any one of [1] to [7], wherein the M β} ion is an ion of a d-block transition metal or an ion of an f-block transition metal.
[9] The metal-organic framework according to any one of [1] to [8], wherein the _{M β ion satisfies the following requirements 1 and 2.}
Requirement 1: A monovalent, divalent or trivalent metal ion capable of forming a complex having a polyhedral molecular structure having a coordination number of 4 or more.
Requirement 2: The ionic radius is 70 to 120 pm.
[10] The metal-organic structure according to any one of [1] to [9], wherein the cubane-type structure in the cluster (β) is a complete cubane-type structure with four nuclei or an incomplete cubane-type structure with three nuclei. body.
[11] The metal-organic structure according to any one of [1] to [10], wherein the cubane-type structure in the cluster (β) further comprises a hydroxide ion as a component.
[12] The metal-organic framework according to any one of [1] to [11], wherein the cluster (β) is represented by the following formula (3).

In formula (3), M _β represents a metal ion constituting a cubane-type structure, and L _β represents a carboxylate ligand. p is an integer of 0 to 10, q is an integer of 0 to 10 (where p + q ≧ 1), and r is ( _{valence of M β} × 4) + (-1 × 4) + (value of _{L β).} It is a number calculated by (number × q).
[13] The ligand L _α ¹ has a carboxylate group, and a coordinate bond is formed between the carboxylate group of _{the ligand L α} ¹ _{and the M β ion. [1]} The metal-organic framework according to any one of [12].
[14] The metal-organic framework according to any one of [1] to [13], wherein the composition formula of the metal-organic structure is represented by the following formula (4).

In formula (4), A represents a cation or anion. {(M _β ) ₄ (OH) ₄ (H ₂ O) _p (L _β ) _q } is an r-valent cation, M _β represents a metal ion constituting a cubane-type structure, and L _β is a carboxy. Represents a rate ligand. p is an integer of 0 to 10 and q is an integer of 0 to 10 (where p + q ≧ 1). {(M _α ¹ ) ₄ (M _α ² ) ₄ (L _α ¹ ) ₁₂ (E) _m } is an n-valent anion, and M _α ¹ is a complex having an octahedral molecular structure with a coordination number of 6. Representing a divalent or trivalent metal ion that can be formed, M _α ² represents a monovalent or divalent metal ion that can form a complex with a tetrahedral molecular structure having a coordination number of 4, L _α ^1. represents a coordinating polydentate ligand to M _beta ^{ion, E is, H -, O 2-, S} 2-, Se 2-, Te 2-, F -, Cl -, Br - or I ^- represents a. m is 0 or 1. B represents a solvent molecule, and t is an integer of 20 to 100. y and z are independently numbers greater than 0 and 1 or less, and x is a number satisfying (valence of A × x) + (r × y) − (n × z) = 0.
[15] A method for producing a metal organic structure, in which a metal ion and an anionic polynuclear metal complex containing a polydentate ligand are accumulated to form a crystal lattice, and a cation species is formed in the gap of the crystal lattice. A metal-organic structure having a Cuban-type structure within a metal-organic polymer chain, comprising contacting an existing ionic flow-type ionic solid with a solution containing d-block transition metal ions or f-block transition metal ions. How to make a body.

According to the present invention, a metal-organic framework containing a cubane-type structure, which is suitably used as a functional material, and a method for producing the same are provided.

It is a figure which shows the molecular structure of a cluster (α) [[Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6-]. It is a schematic diagram explaining the cubane type structure in a cluster (β). It is a figure which shows the molecular structure of a cluster (β) [[Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ^5+]. The cluster (α) is [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- , and the cluster (β) is [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ . It is a figure which shows the molecular structure of a certain metal organic structure. 5 is a powder X-ray diffraction pattern of the metal-organic framework obtained in Examples 1 to 8. It is a figure which shows the cubane type structure in the metal-organic framework obtained in Examples 1-8. It is a figure which shows the result of the DC magnetic susceptibility measurement of the metal-organic framework obtained in Examples 2-8. It is a graph which shows the light emitting property of the metal-organic framework obtained in Example 12. 6 is a graph (comparison of magnetic field change rates at 4K) showing the magnetic refrigeration characteristics of the metal-organic framework obtained in Example 8. 6 is a graph showing the magnetic refrigeration characteristics of the metal-organic framework obtained in Example 8 (comparison by initial temperature at 2.2 T / min).

Hereinafter, the present invention will be described in detail by dividing it into 1) a metal-organic framework and 2) a method for producing a metal-organic structure.

1) metal-organic structure metal organic structure of the present invention is a cluster (alpha) and clusters (beta) metal organic structure containing a structural unit, respectively, the cluster (alpha) is a metal ion (M _alpha ion), and those comprising a ligand (ligand L _alpha) coordinating to M _alpha ions, clusters (beta) is cubane-type of the metal ion (M _beta ions) the essential components is intended to include a structure, at least one ligand L _alpha is a polydentate ligand coordinating to M _beta ions (ligand L _alpha ^1), a metal organic structures.

As described above, the components of the present invention may be omitted in the present specification. The omitted descriptions are as follows.
“ _Mα ion” represents a metal ion in a cluster (α).
"Ligand L _alpha" represents a ligand in the cluster (alpha), in the ligand L _alpha, M ligand coordinating to _β ion L _alpha to "ligand L _alpha ¹ "is expressed.
“M _β ion” represents a metal ion constituting a cubane-type structure in a cluster (β).

In the present invention, the "cluster" refers to an atomic group consisting of a plurality of metal ions and a plurality of ligands, which form a structural unit of a metal-organic framework.
Further, in explaining the present invention, "cluster (α)" or "aggregate of clusters (α)" may be used. The former represents a structural unit of a metal-organic framework [one cluster (α)], and the latter is composed of all clusters (α) in the metal-organic framework (that is, an “aggregate of clusters (α)”). Is an ideological one that remains when elements other than the cluster (α) are eliminated from the metal-organic framework). This also applies to "cluster (β)" and "aggregate of cluster (β)".

[Cluster (α)]
Cluster (alpha) constituting the metal organic structure of the present invention, M _alpha ions, and are those containing a ligand L _alpha, at least one ligand L _alpha is ligand L _alpha ¹ Is.

Examples of the M _α ion include a transition metal ion and a metal ion of a main group element. Among these, transition metal ions or metal ions of Group 12 of the periodic table are preferable as _{M α} ions because stable metal-organic structures can be efficiently formed.

_{The number of M α} ions contained in the cluster (α) is preferably 4 to 15, more preferably 6 to 10.
_{When the number of M α} ions contained in the cluster (α) is small, the cluster (α) tends to be small, and when _{the number of M α} ions contained in the cluster (α) is large, the cluster (α) becomes large. Tend. Further, as the cluster (α) becomes larger, the distance between the centers of a certain cluster (α) and the adjacent cluster (α) tends to become longer, so that the cluster (α) having a large cluster (α) as a constituent unit is used. Aggregates of are prone to large spaces between clusters (α).

From the viewpoint of accommodating the cluster (β) in the space generated between the clusters (α), it is preferable that the space generated between the clusters (α) is not too small. On the other hand, _{from the viewpoint of forming a coordination bond between the ligand L α} ¹ and the M _β ion, it is preferable that the space generated between the clusters (α) is not too large.
Since the cluster (α) contains 4 to 15 M _α ions, the cluster (β) can be more stably contained in the space generated between the clusters (α), and the cluster (α) and the cluster (β) can be accommodated more stably. It becomes easy to obtain a more stable metal-organic structure having each of the constituent units.

As will be described later, a preferred example of the molecular structure of the cluster (α) is one similar to the molecular structure of an anionic polynuclear metal complex constituting a known ionic flow type ionic solid (hereinafter, this anionic property). The polynuclear metal complex may be referred to as an "anionic polynuclear metal complex (α)". Examples of the anionic polynuclear metal complex (α) include the anionic dissimilar metals described in WO2018 / 079831 and WO2019 / 208753. Complexes can be mentioned.).
Since it is easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α), _{the number of Mα} ions contained in the cluster (α) is particularly preferably eight.

The phrase "the molecular structure of the cluster (α) and the molecular structure of the anionic polynuclear metal complex (α) are similar" means the number of metal ions contained in the cluster (α) and the anionic polynuclear metal complex (α). And the coordination type (chelate coordination, cross-linking coordination, etc.) of the ligands that coordinate to these metal ions are the same, and the number of coordination atoms that coordinate to these metal ions is substantially the same. It means that they are the same (same except for the coordination of solvent molecules, etc.).
Whether or not the molecular structures of the two molecules are similar can be determined by performing a single crystal X-ray crystal structure analysis.

The cluster (α) may contain one kind of metal ion or two or more kinds of metal ions as _{M α ions.}
Since it is easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α), it is preferable to contain two kinds of metal ions as _{M α ions.}

When the cluster (α) contains two kinds of metal ions, as a combination of the metal ions, a divalent or trivalent metal ion (hereinafter, hereinafter, which can form a complex having an octahedral molecular structure having a coordination number of 6) can be formed. It _{may be referred to as M α} ¹ _{ion) and a monovalent or divalent metal ion (hereinafter referred to as M α} ² ion) capable of forming a complex having a tetrahedral molecular structure having a coordination number of 4. There is.) Is preferable.
By using the metal ions in this combination, it becomes easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α).

The ionic radius of the M _α ¹ ion is usually 60 to 90 pm, preferably 70 to 80 pm.
Ionic radius of M _alpha ² ions is generally 60 ~ 90 pm, preferably 70 ~ 75 pm.
When _{the ionic radius of the M α} ¹ ion and the ionic radius of the M _α ² ion are within the above ranges, it is easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α). Become.
In the present specification, the ionic radius is obtained by Shannon's improvement on the value arranged by Shannon and Prewitt based on the actual measurement (Chemical Handbook Basic Edition, 5th Edition II-887p, Table 16.35). ..

Examples of the M _α ¹ ion include an ion of one kind of metal selected from the group consisting of the metals of Group 8, Group 9, and Group 10 of the periodic table, Cr, and Mn.
Among these, Rh ³⁺ , Ir ³⁺ , or Co ³⁺ is preferable, and Rh ³⁺ or Ir ³⁺ is more preferable _{as the M α} ¹ ion because stable clusters (α) are easily formed. Further, from the viewpoint that the raw material is inexpensive, Co ³⁺ is preferable _{as the M α} ^{1 ion.}

Examples of the M _α ² ion include an ion of one kind of metal selected from the group consisting of the metals of Group 11 and Group 12 of the periodic table.
^{Among these, Zn 2+} , Cu ⁺ or Ag ⁺ is preferable, and Zn ²⁺ is more preferable, because stable clusters (α) are likely to be formed.

Preferred combinations of M _α ¹ ion and M _α ² _{ion (M α} ¹ ion / M _α ² ion) include (Rh ³⁺ / Zn ²⁺ ), (Rh ³⁺ / Cu ⁺ ), (Rh ³⁺ / Ag ⁺ ), and so on. Examples thereof include (Ir ³⁺ / Zn ²⁺ ), (Co ³⁺ / Ag ⁺ ), and (Co ³⁺ / Zn ^2+).

Since it is easy to obtain a cluster (α) having a molecular structure similar to that of the anionic polynuclear metal complex (α), the cluster (α) _{contains four M α} ¹ ions and four M _α ² ions. It is preferable to include it.

The ligand L _α is not particularly limited as long as it can coordinate with the _{M α ion.}
The ligand _Lα may be an electrically neutral ligand or an anionic ligand.
Further, when the ligand L _α has an asymmetric center, the ligand L _α is composed of a mixture of a plurality of types of optical isomers even if it is composed of one kind of optical isomers. There may be.

Electrically neutral ligands include acyclic amines such as diethylamine and triethylamine; nitrogen-containing heterocycles such as pyrrole, pyridine and imidazole; ethers such as acetonitrile and diethyl ether; ketones such as acetone: Hosphins such as triphenylphosphine; nitriles such as acetonitrile; water molecules; and the like can be mentioned.

Anionic ligands include hydride ion; hydroxide ion; oxide ion; sulfide ion; selenium ion; telluride ion; fluoride ion; chloride ion; bromide ion; iodide ion; cyanide. Ions; alcoholoxo ions such as methoxoions; aryloxo ions such as phenoxoions; carboxylate ions such as acetate ions; and the like.

The ligand L _alpha, may be a multidentate ligand having a coordinating group in these ligands one or more. Examples of such a polydentate ligand include diamines such as ethylenediamine; β-diketones such as acetylacetonate ion; picolinate ion; amino acid ligand such as glycinate ion; and the like.
Cluster (alpha) is to the ligand L _alpha may contain one or may contain two or more.

The number of ligands L _alpha included in the cluster (alpha) is generally 5 to 30, preferably 8-20, more preferably 10-15, particularly preferably 12 or 13.
Tend to cluster (alpha) number of ligands L _alpha contained in a small and cluster (alpha) is small, the cluster (alpha) number of ligands L _alpha contained in many a cluster (alpha) is Tends to grow.
As described above, the size of the cluster (α) tends to affect the formation and stabilization of the cluster (β).
Cluster (alpha) is that containing 5 to 30 ligands L _alpha, and cluster (alpha) and clusters (beta) respectively constitutional units, tends stable metal organic structures obtained.

At least one ligand L _alpha is a polydentate ligand coordinating to M _beta ions (ligand L _alpha ^1).
The ligand L _α ¹ is preferably 2 to 5 _{because the ligand L α} ¹ _{coordinates to both the M α} ion and the M _β ion metal ions and a stable metal-organic structure is easily formed. It is a locus ligand, more preferably a tridental or tetradentate ligand.
In particular, since it is easy clusters of molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α) (α) is obtained, the ligand L _alpha ¹ is particularly preferably a tridentate ligand.

Examples of the ligand L _α ¹ include those represented by the following formula (1).

Wherein (1), ^{T 1} represents a first atom (ligand atoms ^{t 1)} or a group containing a coordination atom ^{t 1} coordinating to M _alpha ion, ^{T 2} is coordinated to M _alpha ion Represents a group containing a ^second atom (coordinating atom t ² ) or a coordinating atom t ^{2, where T 3} is an _{atom coordinating to an M β} ion (coordinating atom t ³ ) or a coordinating atom t ³ . Represents a group containing, and G represents a linking group. T ^1- GT ² is an atomic group that forms a 5-membered chelate ring or a 6-membered chelate ring by coordinating the coordination atom t ¹ and the coordination atom t ² to the M _{α ion.}

If T ¹ is a coordinating atom t ^1, coordination atom t ¹ is typically forms part of the anionic groups together with the atoms in G. Similarly, when T ² is a coordination atom t ² or T ³ is a coordination atom t ³ , the coordination atom t ² and the coordination atom t ³ are usually anions together with the atoms in G. It constitutes a part of the sex group.
Examples of such a coordinate atom include an oxygen atom constituting an alcohole group, a sulfur atom constituting a thiolate group, and the like.

When T ¹ is a group containing the coordinating atom t ^{1 , T 1} is usually an anionic group or an electrically neutral group, or is part of a coordinating structure with the atoms in G. Is the basis that constitutes. Similarly, when T ² is a group containing a coordination atom t ^{2 or when T 3} is a group containing a coordination atom t ^{3 , T 2} and T ³ are usually anionic groups or electrically. Is a neutral group, or is a group that forms part of a coordinating structure with the atoms in G.
When T ¹ , T ² , T ³ (hereinafter referred to as "T ¹ etc.") are anionic groups, ^{examples of T 1} etc. include carboxylate groups (coordinating atoms are oxygen atoms). ..
When T ^{1 and the} like are electrically neutral groups, examples of T ^{1 and the} like include an amino group (coordinating atom is a nitrogen atom) and a phosphino group (coordinating atom is a phosphorus atom).
When T ^{1 and the} like are groups that form a part of the coordinating structure together with the atoms in G, the T ^{1 and the} like include an alkoxy group (the coordinating atom is an oxygen atom) and a thioether structure that form an ether structure. Examples thereof include an alkylthio group (coordinating atom is a sulfur atom) constituting the alkylthio group.

Examples of the atom constituting G include a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom.
The number of atoms constituting G (however, excluding hydrogen atoms) is usually 2 to 15, preferably 2 to 10, and more preferably 2 to 5.

T ¹ is preferably a coordination atom that constitutes a part of an anionic group together with an atom in G, and more preferably a sulfur atom that constitutes a thiolate group.
T ² is preferably an electrically neutral group, more preferably an amino group.
T ³ is preferably an anionic group, more preferably a carboxylate group.
Since T ¹ , T ² , and T ³ are the above-mentioned groups, it becomes easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α).

The ligand L _α ¹ is an amino acid ligand (in the present specification, the “amino acid ligand” is an amino acid having a total charge of 0 in addition to a function as a ligand. , Including those in which protonated or deprotonated amino acids function as ligands.).
Since the ligand _Lα ¹ is an amino acid ligand, it is possible to efficiently form a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α).

Examples of the amino acid ligand include those represented by the following formula (5).

In formula (5), R represents an amino acid side chain having ^{T 1 , and r 1} , r ² , and r ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. -N ^(r 1) ^{(r 2)} is, ^T 2 in the formula (1) ^{(t 2} is nitrogen atom) and, -C (O) O ^- is, ^T 3 ^{(t 3} in the formula (1) Is an oxygen atom).

The alkyl groups of r ^{1, r} 2, carbon atoms represented by ^{r 3} 1 ~ 5, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl, t- butyl Groups, isobutyl groups and the like can be mentioned.
Since liable anionic polynuclear metal complex (alpha) of the molecular structure similar to the molecular structure of the cluster (alpha) is obtained, as the ^{r 1, r 2, r 3} , preferably a hydrogen atom or a methyl group, a hydrogen atom More preferred.

Examples of the amino acid ligand include those shown below. In the formula, r ¹ , r ² , and r ³ have the same meanings as described above.

The ligands represented by the formulas (5-1) to (5-5) are ligands in which T ¹ has a negative charge and can form a 5-membered chelate ring.
The ligand represented by the formulas (5-6) and (5-7) is a ligand in which T ¹ has a negative charge and can form a 6-membered chelate ring.
The ligand represented by the formula (5-8) is a ligand in which T ¹ is electrically neutral and can form a 6-membered chelate ring.

Among these, since it is easy to obtain a cluster (α) having a molecular structure similar to the molecular structure of the anionic polynuclear metal complex (α), the coordination represented by the formulas (5-1) to (5-7) is easy to obtain. The child is preferable, because the ligand represented by the formula (5-3), the formula (5-4), or the formula (5-6) stably forms a 5-membered ring or a 6-membered ring together with the metal. preferable. Examples of formula (5-3) include cysteine, examples of formula (5-4) include penicillamine, and formula (5-6) includes homocysteine.

Cluster (alpha) is to the ligand L _alpha ¹ may contain one or may contain two or more.
Number of ligands L _alpha ¹ included in cluster (alpha) is usually 8 to 24, preferably 8 to 16, more preferably 12.

The cluster (α) can be a hydride ion (H ⁻ ), an oxide ion (O ^2- ), a sulfide ion (S ^2- ), a serene product ion (Se ^2- ), and a telluride ion (Te), if necessary. ^2), fluoride ion (F ^-), chloride ion (Cl ^-), bromide ion (Br ^-), and iodide ion (I ^-) ligand selected from the group consisting of (hereinafter, "coordination It may be described as "child E").

Ligand E is a relatively small anion. Coordination of the ligand E to the M _α ion may further stabilize the cluster (α).
Since this effect can be easily obtained, the ligand E is preferably an oxide ion, a sulfide ion, a chloride ion, or a bromide ion, and more preferably an oxide ion or a sulfide ion.

Examples of the cluster (α) include those represented by the following formula (2).

In formula (2), M _α ¹ represents a divalent or trivalent metal ion capable of forming a complex having an octahedral molecular structure having a coordination number of 6, and M _α ² is a tetrahedron having a coordination number of 4. Represents a monovalent or divalent metal ion capable of forming a complex of body type molecular structure, L _α ¹ represents a polydentate ligand that also coordinates with M _β ^{ion, and E represents H −} , O ^{2 -, S 2-, Se 2-,} Te 2-, F -, Cl -, Br - or I ^- it represents a. m is 0 or 1, and n is ( _{valence of M α} ¹ × 4) + ( _{valence of M α} ² × 4) + ( _{valence of L α} ¹ × 12) + (valence of E). It is a number calculated by × m).

_{The M α} ¹ , M _α ² , L _α ¹ , and E of the cluster (α) represented by the equation (2) are as described above, respectively. n is usually an integer of 4 to 14, preferably an integer of 6 to 8.

The molecular structure of the cluster (α) represented by the formula (2) is similar to the molecular structure of the anionic polynuclear metal complex (α) (for example, the molecular structure represented by FIG. 2 of WO2019 / 208753). Can be mentioned.

As an example of the molecular structure of the cluster (α) represented by the formula (2), [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- (L-cys represents a ligand derived from L-cysteine). The molecular structure of (the same applies hereinafter) is shown in FIG.
FIG. 1 (a) shows a metal-organic framework [Lu _0.33 [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] [Rh ₄ Zn ₄ (L-cys) ₁₂ O] · nH ₂ From the results of crystal structure analysis of O (OAc represents acetate ion; the same applies hereinafter)], only the cluster (α) portion ([Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- ) is represented. Is.
FIG. 1 (b) schematically shows [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- .
FIG. 1 (c) shows _{[Lu 4} (OH) ₄ ( _{Lu 4 (OH) 4) forming a coordinate bond between one [Rh 4} Zn ₄ (L-cys) ₁₂ O] ^6- and this cluster (α). H ₂ O) ₇ (OAc) ₃ ] It is a figure showing the relationship of the cubane type structure in ^5+.

As shown in FIGS. 1 (a) to 1 (c), the carboxylate oxygen of the L-cysteine-derived ligand (L-cys) constituting _{[Rh 4} Zn ₄ (L-cys) ₁₂ O] ^6-. The atom is not coordinated to the Rh ion or Zn ion, and forms a coordinate bond with the Lu ion _{in [Lu 4} (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ^5+. Can be done.

The aggregate of clusters (α) constituting the metal-organic framework of the present invention is formed by regularly arranging the clusters (α).
The aggregate of clusters (α) is preferably derived from the anion portion of the ionic flow type ionic solid.

The "ionic solid" means a solid containing a cationic species and an anionic species as essential constituents.
The "ionic flow type ionic solid" means an ionic solid having ionic fluidity. Examples of the ionic flow type ionic solid include those in which anionic polynuclear metal complexes are accumulated to form a crystal lattice and a cationic species is present in the gaps between the crystal lattices. "Cation species are present in the gaps of the crystal lattice" means that the anionic polynuclear metal complex is bound to a specific position forming the crystal lattice, whereas the cation species is a free position in the gaps of the crystal lattice. Refers to the state that exists in. Since it has such a structure, this ionic flow type ionic solid has a cation exchange ability.

Examples of the metal ion constituting the anionic polynuclear metal complex include the same as those described as _{the M α ion.}
The multidentate ligand constituting the anionic polynuclear metal complexes include the same as described as ligands L ^1.

As the anionic polynuclear metal complex, a known complex can be used. Examples of known complexes include the anionic dissimilar metal complexes described in WO2018 / 079831 and WO2019 / 208753.

Examples of the cation species constituting the ionic flow type ionic solid include metal ions.
Specific examples of the cation species include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ^{2+ and the} like. ^{Among these, Na +} , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , and Ba ²⁺ are preferable, and Na ⁺ or K is preferable because the metal-organic framework of the present invention can be obtained more efficiently. ⁺ Is more preferable.

As the ionic flow type ionic solid, for example, the ionic solid described in WO2018 / 079831 and WO2019 / 208753 can be preferably used.

By using the anion portion of an ionic flow type ionic solid as an aggregate of clusters (α), a metal-organic polymer chain of a metal-organic framework can be efficiently formed.

[Cluster (β)]
The cluster (β) constituting the metal-organic structure of the present invention includes a cubane-type structure in which _{a metal ion (M β ion) is an essential component.}

Examples of the M _β ion include an ion of a d-block transition metal or an ion of an f-block transition metal.
Specific examples of d-block transition metal ions include Sc ³⁺ , Co ²⁺ , Ni ²⁺ , Cu ⁺ , Y ^{3+ and the} like.
Specific examples of f-block transition metal ^{ion, La 3+, Ce 3+, Pr} 3+, Nd 3+, Pm 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+, Tm 3+ , Yb ³⁺ , Lu ^{3+ and the} like.
^{Among these, Tb 3+} is preferable when the metal-organic framework of the present invention is used as a light emitting material ^{, and Gd 3+} is preferable when it is used as a magnetic refrigeration material.

Since it is easy to obtain a more stable metal-organic framework having clusters (α) and clusters (β) as constituent units, M _β ions preferably satisfy the following requirements 1 and 2.
Requirement 1: A monovalent, divalent or trivalent metal ion capable of forming a complex having a polyhedral molecular structure having a coordination number of 4 or more.
Requirement 2: The ionic radius is 70 to 120 pm.

When the M _β ion satisfies the requirement 1, a more stable cubane-type structure is easily formed.
When the M _β ion satisfies the requirement 2, clusters (β) having an appropriate size are formed, and a more stable metal-organic structure can be obtained.

_{The number of M β} ions contained in the cluster (β) is usually 3 or 4.
The cluster (β) may have metal ions that do not form a cubane-type structure.
The total number of metal ions contained in the cluster (β) is preferably 3 to 10, more preferably 3 to 6.

As described above, the cluster (β) occupies the space generated between the clusters (α). Further, the cluster (β) forms a part of the metal-organic polymer chain of the metal-organic framework by forming a coordinate bond between the _{M β} ion and the ligand L _α ^1. Become.
When the cluster (β) contains 3 to 10 metal ions, it becomes easy to obtain a stable metal-organic structure having the cluster (α) and the cluster (β) as constituent units, respectively.

Examples of the cubane-type structure in the cluster (β) include a complete cubane-type structure with four nuclei and an incomplete cubane-type structure with three nuclei.
A schematic diagram of a complete cubane-type structure of four nuclei is shown in FIG. 2 (a). Among the eight vertices of the hexahedron, _{metal ions occupy the place indicated by M β} , and the remaining vertices are between two or more metal ions such as hydroxide ion and oxide ion. Is occupied by a ligand that bridges with one atom.), A complete Cuban-type structure is formed.
The hexahedron shown in FIG. 2A is a cube, but the four-core complete cubane-type structure may be represented by a hexahedron other than the cube.

A schematic diagram of the incomplete cubane-type structure of the three nuclei is shown in FIG. 2 (b). The 3-nucleus incomplete cubane-type structure is a structure in which one metal ion and the monatomic cross-linking ligand coordinated to the metal ion are removed from the 4-nucleus complete cubane-type structure.

The monoatomic bridging ligands constituting the cubane-type structure in the cluster (β) include hydroxide ion (OH ⁻ ), oxide ion (O ^2- ), and alcohol ion (RO ⁻ , R are alkyl groups. ), Sulfide ion (S ^2- ) and the like. Of these, hydroxide ions are preferred.

As the cubane-type structure, a four-nucleus complete cubane-type structure is preferable because the cluster (β) is more stabilized.
When the M _β ion satisfies the following requirements 1'and 2', a cluster (β) having a complete cubane-type structure of four nuclei is easily formed.
Requirement 1': A divalent or trivalent metal ion capable of forming a complex having a polyhedral molecular structure having a coordination number of 5 to 8.
Requirement 2': The ionic radius is 75 to 115 pm.

The cluster (β) may contain a ligand other than the monatomic cross-linking ligand constituting the cubane-type structure.
The monoatomic ligands other than bridging ligands constituting the cubane-type structure, those exemplified as the ligand L _alpha (excluding monoatomic bridging ligands described above) can be mentioned.
The cluster (β) has a carboxylate ligand because a more stable cluster (β) can be easily obtained when the coordination number of _{M β ions is large (for example, the coordination number is 7 or 8).} Is preferable.
Examples of the carboxylate ligand include acetate ion, propionate ion, benzoate ion and the like.
The carboxylate ligand may function as a cross-linking ligand that bridges between _{two or more M β ions.}

Examples of the cluster (β) include those represented by the following formula (3).

In formula (3), M _β represents a metal ion constituting a cubane-type structure, and L ² represents a carboxylate ligand. p is an integer of 0 to 10, q is an integer of 0 to 10 (where p + q ≧ 1), and r is ( _{valence of M β} × 4) + (-1 × 4) + (value of ^{L 2).} It is a number calculated by (number × q).

_{The M β} and L ² of the cluster (β) represented by the equation (3) are as described above, respectively. r is usually an integer of 4 to 6.

As an example of the molecular structure of the cluster (β) represented by the formula (3), the molecular structure of [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ is shown in FIG.
FIG. 3A shows a metal-organic framework (Lu _0.33 [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] [Rh ₄ Zn ₄ (L-cys) ₁₂ O] · nH ₂ From the result of the crystal structure analysis of O), only the part of the cluster (β) ([Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ ) is shown.
FIG. 3 (b) schematically shows [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ .

As shown in FIGS. 3 (a) and 3 (b), [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ is composed of 4 Lu ions and 4 hydroxoions. It has a complete cubane-type structure with four nuclei. In addition, the acetate ion functions as a cross-linking ligand that bridges between the two Lu ions.
Although not shown in FIG. 3, there are three [Rh ₄ Zn ₄ (L-cys) _{12 around one [Lu 4} (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ^5+. O] ^6- exists. Then, the carboxylate group of the cysteine ligand contained therein crosslinks between the two Lu ions like the above-mentioned acetate ion [FIG. 1 (c)].

[Metal-organic framework]
The metal-organic framework of the present invention contains the cluster (α) and the cluster (β) as a constituent unit, and the ligand _Lα ¹ in the cluster (α) is a cubic of the cluster (β). It is also coordinated with _{metal ions (M β} ions) contained in the mold structure.

The ligand L _α ¹ crosslinks the M _α ion and the M _β ion to form a stable metal-organic framework.
When the ligand L _α ¹ has a carboxylate group, it is preferable that the carboxylate group of _{the ligand L α} ¹ _{is coordinated to the M β ion.} Since the _{coordinating group that coordinates with the M β} ion is a carboxylate group, a more stable metal-organic structure can be easily formed.

As mentioned above, the size of the clusters (α) usually affects the size of the space created between the clusters (α). Also, the size of the space created between the clusters (α) affects the stability of the clusters (β).
Therefore, the cluster (β) is stabilized by adjusting the number and types of metal ions (M _α ions) and ligands L _α that compose the cluster (α) and optimizing the size of the cluster (α). It is preferable to make it.

When the cluster (α) is formally represented as one sphere in consideration of the spread of atoms constituting the cluster (α), such a sphere (hereinafter, may be referred to as “sphere (α)”). The diameter of is usually 1.0 to 3.0 nm, preferably 1.2 to 2.0 nm.
The diameter of the sphere (α) can be calculated based on the result of single crystal X-ray crystal structure analysis.
For example, when the cluster (α) has the molecular structure shown in FIG. 1, the atom located at the farthest position from the center of the cluster (α) is the oxygen atom of the carboxylate group, and therefore a certain carboxy. The value of the longest distance between the oxygen atom of the rate group and the oxygen atom of another carboxylate group can be mimicked as the diameter of the sphere (α).
Specifically, with respect to the metal-organic framework obtained in the examples described later, the diameter of the sphere (α) corresponding to _{[Rh 4} Zn ₄ (L-cys) ₁₂ O] ^{6- is 1.537 nm.} , [Ir ₄ Zn ₄ (L-cys) ₁₂ O] The diameter of the sphere (α) corresponding to ^{6- is 1.550 nm.}

The value of the ratio of the diameter of the sphere (α) to _{the radius of the M β} ion [sphere (α) / M _β ion] is usually 14.0 to 19.0, preferably 14.2 to 18.5, more preferably. It is 14.6 to 17.3. When the value of the ratio of the diameter of the sphere (α) to _{the radius of the M β} ion is within the above range, a more stable metal-organic structure can be easily obtained.

As described above, the size of the cluster (α) can be changed by adjusting the number and types of the metal ions (M _α ions) and the ligand L _{α constituting the cluster (α).}
For example, with respect to the anionic dissimilar metal complex [[Rh ₄ Ag ₄ (L-cys) ₁₂ ] ^8- ] constituting the ionic solid described in Patent Document 1, the one corresponding to the diameter of the sphere (α) is used. It was calculated to be 1.567 nm. Therefore, clusters (α) derived from this anionic heterogeneous metal complex are expected to be suitable for stabilizing metal-organic frameworks containing _{larger M β ions.}

Examples of the composition formula representing the metal-organic framework include those represented by the following formula (4).

In formula (4), A represents a cation or anion. {(M _β ) ₄ (OH) ₄ (H ₂ O) _p (L _β ) _q } is an r-valent cation, M _β represents a metal ion constituting a cubane-type structure, and L _β is a carboxy. Represents a rate ligand. p is an integer of 0 to 10 and q is an integer of 0 to 10 (where p + q ≧ 1). {(M _α ¹ ) ₄ (M _α ² ) ₄ (L _α ¹ ) ₁₂ (E) _m } is an n-valent anion, and M _α ¹ is a complex having an octahedral molecular structure with a coordination number of 6. Representing a divalent or trivalent metal ion that can be formed, M _α ² represents a monovalent or divalent metal ion that can form a complex with a tetrahedral molecular structure having a coordination number of 4, L _α ^1. represents a coordinating polydentate ligand to M _beta ^{ion, E is, H -, O 2-, S} 2-, Se 2-, Te 2-, F -, Cl -, Br - or I ^- represents a. m is 0 or 1. B represents a solvent molecule, and t is an integer of 20 to 100. y and z are independently numbers greater than 0 and 1 or less, and x is a number satisfying (valence of A × x) + (r × y) − (n × z) = 0.

_{{(M β} ) ₄ (OH) ₄ (H ₂ O) _p (L _β ) _q } and {(M _α ¹ ) ₄ (M _α ² ) ₄ (L) in the composition formula represented by the formula (4). _α ¹ ) ₁₂ (E) _m } is as described above.
When A is a cation, such A includes Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , Co ²⁺ , ^{Ni 2+, Sc 3+, Y 3+} , La 3+, Ce 3+, Pr 3+, Nd 3+, Pm 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+, Tm 3+, Yb 3+ , Lu ^{3+ and the} like.
If A is an anion, as such ^{A, O 2-, S 2-,} Se 2-, Te 2-, F -, Cl -, Br -, I -, OH -, OAc - ( acetate ion ) Etc. can be mentioned.
B is the solvent molecule used for the synthesis. Examples of B include water; alcohols such as methanol and ethanol; ketones such as acetone; ethers such as diethyl ether and tetrahydrofuran; nitriles such as acetonitrile; halogenated hydrocarbons such as chloroform; and the like.

As an example of the molecular structure of the metal-organic framework having the composition formula represented by the formula (4), the cluster (α) is [Rh ₄ Zn ₄ (L—cys) ₁₂ O] ^6- , and the cluster (β). ) Is [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ . The molecular structure of the metal-organic framework is shown in FIG.

FIG. 4A is a packing structure diagram of crystals of a metal-organic framework.
FIG. 4B is a schematic diagram of crystals of a metal-organic framework. [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- is represented by a pink sphere, and [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ is represented by an orange sphere. There is.
FIG. 4 (c) shows one [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^6- and three [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ^{5+ around it.} Is a diagram showing how is forming a coordination bond.
FIG. 4 (d) shows one [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ and three [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ^{6- around it.} Is a diagram showing how is forming a coordination bond.

As shown in FIGS. 4 (a) to 4 (d), this metal-organic framework is composed of [Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ ] ⁵⁺ and [Rh ₄ Zn ₄ (L-). cys) ₁₂ O] It has a metal-organic polymer chain formed by a coordination bond between ^6-.

The metal-organic framework of the present invention has a cubane-type structure in which a _{metal ion (M β ion) is an essential component in a metal-organic polymer chain.}
Therefore, the metal-organic framework of the present invention can be suitably used as a magnetic material such as a magnetic refrigeration material, a light emitting material, and a functional material such as a catalyst material.

The magnetic refrigeration material is a substance that has a magnetic refrigeration effect. The magnetic refrigeration effect is a cooling method that utilizes a change in entropy due to a magnetic field. That is, when a magnetic field is applied to a magnetic refrigerated material, the magnetic moments caused by the unpaired electrons of atoms (ions) are regularly aligned in the direction of the magnetic field lines, and the reduced entropy is released as heat. On the other hand, when the magnetic field is removed from the magnetic refrigerated material, the direction of the magnetic moment becomes irregular and the entropy increases, so that the temperature of the magnetic refrigerated material decreases in the adiabatic state. By using this cycle, the surroundings can be cooled efficiently.

In general, the ⁴ He is used as a refrigerant, it is possible to realize a very low temperature of about 2K.
The metal-organic framework of the present invention is suitably used as a magnetic refrigeration material under such cryogenic conditions.
That is, the cluster (β) constituting the metal-organic structure of the present invention contains a cubane-type structure, but when metal ions having unpaired electrons form a cubane-type structure, interaction between spins is unlikely to occur. .. Therefore, in the metal-organic framework of the present invention, the change in magnetic entropy due to the magnetic field operation is large mainly in the temperature region of about 2K or less, which makes it suitable as a magnetic refrigerating material under the above-mentioned extremely low temperature conditions.
Further, in the metal-organic framework of the present invention, the cubane-type structure is stabilized and the cubane-type structure is regularly integrated. These points are also considered to have a favorable effect on the magnetic refrigeration effect.

When the metal-organic structure of the present invention is used as a magnetic refrigeration material, Gd ³⁺ ions are preferable as the metal ions contained in the cubane-type structure. Since the Gd ³⁺ ion has a large spin quantum number and a high maximum spin degree of freedom, it has a high responsiveness to a magnetic field and a large change in magnetic entropy. Therefore, it is easy to obtain a magnetic refrigeration material having a larger cooling capacity.

2) Method for producing a metal-organic structure The method for producing a metal-organic structure of the present invention is a method for producing a metal-organic structure having a Cuban-type structure in a metal-organic polymer chain, and is a method for producing a metal ion and a metal-organic structure. Anionic polynuclear metal complexes containing polydentate ligands accumulate to form a crystal lattice, and an ionic flow type ionic solid in which a cation species exists in the gaps of the crystal lattice is an ion of a d-block transition metal or an f-block. It has a step of contacting with a solution containing an ion of a transition metal.

Examples of the ionic flow type ionic solid include those similar to those previously shown in the description of the invention of the metal-organic framework.
Examples of the d-block transition metal ion and the f-block transition metal ion include the same as those previously shown in the description of the invention of the metal-organic framework.

A solution containing d-block transition metal ions or f-block transition metal ions can be prepared by dissolving a salt of d-block transition metal ions or a salt of f-block transition metal ions in an appropriate solvent. ..
The anion contained in the salts ^{thereof, F -, Cl -, Br} -, I -, OAc -, NO 3 -, SO 4 2- , and the like.

The solvent of the solution containing the metal ion for forming the cubane type structure is not particularly limited as long as it does not dissolve the ionic flow type ionic solid or the metal-organic structure of the present invention. A mixed solvent may be used to adjust the solubility of the ionic flow type ionic solid or the metal-organic framework. Specific examples of the solvent used include water; alcohols such as methanol, ethanol, propyl alcohol, and isopropyl alcohol; and a mixed solvent of water and alcohols; and the like.

In the step of contacting the ionic flow type ionic solid with the solution containing the metal ion for forming the cubane type structure, the contact operation, the contact time, and the contact temperature are not particularly limited.
For example, an ionic flow type ionic solid is immersed in a solution containing a metal ion for forming a cubane type structure, and is left as it is at around room temperature (for example, 5 to 25 ° C.) for 1 day to 1 month, preferably about 1 week. By standing still, the metal-organic structure of the present invention can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[Synthesis Example 1] K ₆ [Rh ₄ Zn ₄ (L-cys) ₁₂ O] ・ Synthesis of 47.5H ₂ O According to the method described in Example 1 of WO2019 / 208753, K ₆ [Rh ₄ Zn ₄ (Synthesis Example 1) L-cys) ₁₂ O] · 47.5H ₂ O (hereinafter, may be referred to as “ionic flow type ionic solid (1)”) was synthesized.
The ionic flow type ionic solid (1) was a yellow solid.

[Synthesis Example 2] K ₆ [Ir ₄ Zn ₄ (L-cys) ₁₂ O] · 40H ₂ O Synthesis In Synthesis Example 1, Δ-H ₃ [Rh (L-cys) ₃ ] is replaced with Δ-. _{K 6} [Ir ₄ Zn ₄ (L-cys) ₁₂ O] · 40H ₂ O (hereinafter, “ion”, in the same manner as in Synthesis Example 1 except that H ₃ [Ir (L-cys) _{3] was used.} It may be described as "flowable ionic solid (2)").

In Synthesis Example 3] _{K 8 [Rh 4 Ag 4 (} L-cys) 12] · nH 2 O Example 1 Synthesis WO2018 / 079831, and except for using potassium hydroxide instead of lithium hydroxide, according to the method described in example 1 of _{WO2018 / 079831, K 8 [Rh} 4 Ag 4 (L-cys) 12] · nH 2 O ( hereinafter, may be referred to as "ion fluidized ionic solid (3)" There is.) Was synthesized.

It should be noted that other ionic fluid solids can also be manufactured with reference to, for example, WO2019 / 208753 and WO2018 / 079831.

The following analysis was performed on the metal-organic frameworks obtained in the following examples.
[Fluorescent X-ray analysis]
The measurement sample was introduced into a polytetrafluoroethylene sample cell with a Mylar film attached, and X-ray fluorescence analysis was performed under vacuum using an energy dispersive X-ray fluorescence analyzer (EDX-7000, manufactured by Shimadzu Corporation). Was done.
From the obtained strengths of Ln, Zn, and K, the number of lanthanoid atoms (Ln / Zn) with respect to the number of zinc atoms and the number of potassium atoms (K / Zn) with respect to the number of zinc atoms were calculated.
Since the number of zinc atoms contained in the cluster (α) of the metal-organic framework synthesized in the examples is 4, if Ln / Zn is a value near 1, the metal-organic framework is cluster (α). It is expected to have a cubane-type structure of four nuclei with the same amount.
Further, from the value of K / Zn, it can be seen to what extent the structure similar to the ionic flow type ionic solid of the starting material remains.
Regarding the "metal-organic framework having a cubane-type structure" obtained in the examples described later, fluorescent X-ray analysis was performed on the products in all the examples, and the analysis results were used to determine the composition.

[Powder X-ray diffraction]
A powder sample was introduced into a capillary tube and sealed. X-rays were irradiated while rotating the capillary tube, and a powder X-ray diffraction image was obtained.
As a measuring device, a powder X-ray diffractometer equipped in SPring-8 BL02B2 was used (λ = 1.0 Å, detector: MYTHEN microtrip X-ray detector, manufactured by Detector).
When a sharp diffraction image is shown, it can be seen that the solid has crystallinity.
In particular, regarding the metal-organic framework obtained in the examples, when the peak derived from the (111) plane appearing near 2θ = 4 ° is smaller than the peak derived from the (200) plane appearing near 2θ = 5 °, It suggests that a cubane-type structure is formed.
The measurement results for the metal-organic frameworks obtained in Examples 1 to 8 are shown in FIG.

[Single crystal X-ray crystal structure analysis]
A single crystal X-ray crystal structure analysis was performed on the metal-organic framework under a nitrogen stream adjusted to a temperature of 100 K.
As a measuring device, a single crystal X-ray diffractometer equipped in Pohang Accelerator Laboratory (PAL, Pohang City, South Korea) BL-2D was used (λ = 0.62997Å, detector: MX225HS, manufactured by Rayonic).
The cubane-type structure in the metal-organic framework obtained in Examples 1 to 8 is shown in FIG.
Regarding the "metal-organic framework having a cubane-type structure" obtained in the following examples, single crystal X-ray crystal structure analysis was also performed on those obtained in examples other than Examples 1 to 8. I confirmed the structure.

[Example 1]
Ion flow type ionic solid (1) 100 mg _{was immersed in 20 mL of 0.02 M lutetium acetate [Lu (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] and allowed to stand as it was. After 1 week, the supernatant was removed by decantation, and the remaining yellow solid was immersed in 20 mL of a 0.1 M lutetium acetate aqueous solution and allowed to stand for another week.
The solid was then collected by filtration and dried. The yield was 100 mg (yield 90%).
As a result of fluorescent X-ray analysis, powder X-ray diffraction, and single crystal X-ray crystal structure analysis, the obtained solid is a metal-organic framework having a Cuban-type structure [Lu _0.33 [{Lu ₄ (OH) ₄ ( H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O].

[Example 2]
In Example 1, the same procedure as in Example 1 except that ytterbium acetate [Yb (OAc) ₃ ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Yb _0.33 [{Yb ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 3]
In Example 1, the same procedure as in Example 1 _{except that a thulium acetate [Tm (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Tm _0.33 [{Tm ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 4]
In Example 1, the same procedure as in Example 1 _{except that an erbium acetate [Er (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with cubane-type structure [Er _0.33 [{Er ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 5]
In Example 1, the same procedure as in Example 1 _{except that a holmium acetate [Ho (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Ho _0.33 [{Ho ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 6]
In Example 1, the same procedure as in Example 1 _{except that a dysprosium acetate [Dy (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Dy _0.33 [{Dy ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 7]
In Example 1, the same procedure as in Example 1 _{except that a terbium acetate [Tb (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metal-organic framework with cubane-type structure [Tb _0.33 [{Tb ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 8]
In Example 1, the same procedure as in Example 1 _{except that a gadolinium acetate [Gd (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Gd _0.33 [{Gd ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 9]
100 mg of the ionic flow type ionic solid (1) _{was immersed in 20 mL of a 0.1 M cobalt acetate [Co (OAc) 2} ] solution [water / ethanol (v / v = 1/3)] and allowed to stand as it was. After 1 week, the supernatant was removed by decantation, and the remaining pink solid was immersed in a water / ethanol mixed solvent (v / v = 1/3) and allowed to stand for another week.
The solid was then collected by filtration and dried. The yield was 100 mg (90%).
As a result of fluorescent X-ray analysis, powder X-ray diffraction, and single crystal X-ray crystal structure analysis, the obtained solid is a metal-organic framework having a Cuban-type structure [Co [{Co ₄ (OH) ₄ (H ₂ O). ) ₉ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O].

[Example 10]
In Example 9, the same procedure as in Example 9 _{except that a nickel acetate [Ni (OAc) 2} ] solution [water / ethanol (v / v = 1/3)] was used instead of the cobalt acetate solution. , A metal organic structure having a Cuban-type structure [Ni [{Ni ₄ (OH) ₄ (H ₂ O) ₉ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 11]
In the same manner as in Example 9 except that a copper acetate [Cu (OAc) ₂ ] solution [water / ethanol (v / v = 1/3)] was used instead of the cobalt acetate solution. , A metal organic structure having a Cuban-type structure [Cu [{Cu ₄ (OH) ₄ (H ₂ O) ₉ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 12]
A metal-organic structure having a cubane-type structure is the same as in Example 7, except that the ionic flow-type ionic solid (2) is used instead of the ionic flow-type ionic solid (1) in Example 7. The body [[{Tb ₄ (OH) ₄ (OAc) ₂ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 13]
A metal organic structure having a cubane-type structure in the same manner as in Example 1 except that the ionic flow type ionic solid (2) was used instead of the ionic flow type ionic solid (1) in Example 1. The body [Lu _0.33 [{Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 14]
In Example 13, the same procedure as in Example 13 except that ytterbium acetate [Yb (OAc) ₃ ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Yb _0.33 [{Yb ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 15]
In Example 13, the same procedure as in Example 13 _{except that a thulium acetate [Tm (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Tm _0.33 [{Tm ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 16]
In Example 13, the same procedure as in Example 13 _{except that an erbium acetate [Er (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with cubane-type structure [Er _0.33 [{Er ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 17]
In Example 13, the same procedure as in Example 13 _{except that a holmium acetate [Ho (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Ho _0.33 [{Ho ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 18]
In Example 13, the same procedure as in Example 13 _{except that a dysprosium acetate [Dy (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Dy _0.33 [{Dy ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 19]
In Example 13, the same procedure as in Example 13 _{except that a gadolinium acetate [Gd (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure with Cuban-type structure [Gd _0.33 [{Gd ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}] · nH ₂ O] was obtained.

[Example 20]
Same as in Example 1 except that ytterbium propionate [Yb (OAc) ₃ ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. A metal organic structure having a Cuban-type structure [Yb _0.33 [{Yb ₄ (OH) ₄ (H ₂ O) ₇ (OPr) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}]. nH ₂ O] was obtained.

[Example 21]
A metal-organic structure having a cubane-type structure in the same manner as in Example 1 except that the ionic flow type ionic solid (3) was used instead of the ionic flow type ionic solid (1) in Example 1. Body [Lu [{Lu ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Ag ₄ (L-cys) ₁₂ }]. nH ₂ O] was obtained.

[Example 22]
In Example 21, the same procedure as in Example 21 except that ytterbium acetate [Yb (OAc) ₃ ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure having a Cuban-type structure [Yb [{Yb ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Ag ₄ (L-cys) ₁₂ }]. nH ₂ O] was obtained.

[Example 23]
In Example 21, the same procedure as in Example 21 _{except that a thulium acetate [Tm (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure having a Cuban-type structure [Tm [{Tm ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Ag ₄ (L-cys) ₁₂ }]. nH ₂ O] was obtained.

[Example 24]
In Example 21, the same procedure as in Example 21 _{except that an erbium acetate [Er (OAc) 3} ] solution [water / ethanol (v / v = 1/3)] was used instead of the lutetium acetate solution. , Metallic organic structure having a Cuban-type structure [Er [{Er ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Ag ₄ (L-cys) ₁₂ }]. nH ₂ O] was obtained.

[Measurement of magnetic susceptibility]
Using the metal-organic frameworks obtained in Examples 2 to 8 as measurement samples, the DC magnetic susceptibility was measured under the conditions of a magnetic field of 0.1 T and a temperature range of 2-300 K.
As a measuring device, MPMS-2 (manufactured by Quantum Design Co., Ltd.) was used.
The measurement results are shown in FIG.

[Light emission characteristics]
Using the metal-organic framework obtained in Example 12 [[{Tb ₄ (OH) ₄ (OAc) ₂ } {Ir ₄ Zn ₄ (L-cys) ₁₂ O}]], nH ₂ O] as a solid sample. , The emission characteristics were investigated.
A fluorescence spectrophotometer, FP-8500 (manufactured by JASCO Corporation) was used as a measuring device, and measurement was performed at room temperature (25 ° C.).
The emission spectrum was measured at an excitation wavelength of 350 nm, and the excitation spectrum was measured at an emission wavelength of 544 nm.
The measurement results are shown in FIG. In FIG. 8, the spectrum in the range of 420 to 750 nm (red line) is the emission spectrum, and the spectrum in the range of 250 to 480 nm (black line) is the excitation spectrum.
Sharp signal emission spectra are all attributed with emission from ^{Tb 3+} ions ^{_{(489nm: 5 D 4 → 7}} F 6, 544nm: 5 D 4 → 7 F 5, 584nm: 5 D 4 → 7 F 4, 620 nm: ⁵ D ₄ → ⁷ F ₃ ).

Metal-organic framework obtained in Example 8 [Gd _0.33 [{Gd ₄ (OH) ₄ (H ₂ O) ₇ (OAc) ₃ } {Rh ₄ Zn ₄ (L-cys) ₁₂ O}]. Using nH ₂ O] as a solid sample, the magnetic refrigeration effect was investigated as follows.
In order to prevent the temperature change due to the eddy current of the metal material, two 10 kΩ ruthenium oxide resistance thermometers (one for the sample and one for reference) were installed on the cell stage (diameter 2 cm) made of Bakelite, which is an insulating material, and a hot bath was prepared. .. A 136.9 μg solid sample was placed in a resistance thermometer for the samples constituting the heat bath. This heat bath was introduced into a superconducting magnet (8T manufactured by Cryogenics, UK) set at each temperature of 2.0-10.0K, and a magnetic field was applied from 0T to 5T at a speed of 2.2T / min. A temperature rise of 2.33 K was observed. Further, after confirming that the temperature was cooled to 4.0 K while maintaining the application of 5 T, a temperature drop of 2.76 K was observed when the magnetic field was reduced from 5 T to 0 T at a speed of 2.2 T / min. Further, when the sweep speed of the magnetic field was increased to 3.54 T / min, the temperature drop increased up to 3.26 K, and the sample temperature reached 0.74 K, which was 1 K or less. The changes in the magnetic field and temperature are shown in FIGS. 9 and 10.
As described above, by using the metal-organic framework of the present invention, it is possible to create an extremely low temperature of 1 K or less by applying a magnetic field without using ^{3 He or the like.} This temperature change indicates the existence of a magnetic refrigeration effect derived from Gd ions in the sample, which has a large magnetic moment due to the cubane structure but does not cause order formation and is paramagnetic.

[Reference Example 1] K ₆ [Co ₄ Zn ₄ (L-cys) ₁₂ O] ・_{Synthesis of nH 2} O According to the method described in Example 2 of WO2018 / 079831, K ₆ [Co ₄ Zn ₄ (L-). cys) ₁₂ O] ・ nH ₂ O was synthesized.

[Reference Example 2] K ₈ [Co ₄ Ag ₄ (L-cys) ₁₂ ] ・_{Synthesis of nH 2} O According to the method described in Example 3 of WO2018 / 079831, K ₈ [Co ₄ Ag ₄ (L-cys) ) _12] · nH the ₂ O was synthesized.

Reference Example 3] _{Na 8 [Rh 4 Cu 4 (} L-cys) 12] · nH 2 O synthesis in Chem. Common. , 2021, 57, 5386-5389 to synthesize the compound of interest. That is, _{a 1: 1 mixture of Δ-H 3} [Rh (L-cys) ₃ ] and CuCl was treated with an aqueous solution of sodium hydroxide and a predetermined operation was performed to perform Na ₈ [Rh ₄ Cu ₄ (L-cys). _12] · nH the ₂ O was synthesized.

[Reference Example 4] _{Synthesis of Na 8} [Rh ₄ Cu ₄ (L-cys) ₁₂ O] and nH ₂ O Similar to Reference Example 3 except that _{CuCl 2} was used instead of CuCl in Reference Example 3. An operation was performed to synthesize _{Na 8} [Rh ₄ Cu ₄ (L-cys) ₁₂ O] and nH _{2 O.}

[Reference Example 5] _{Synthesis of Na 6} [Ir ₄ Cu ₄ (L-cys) ₁₂ ] and nH ₂ O In Reference Example 3, Δ-H ₃ is used instead of Δ-H ₃ [Rh (L-cys) _3]. The same operation as in Reference Example 3 was carried out except that [Ir (L-cys) _{3 ] was used, and Na 6} [Ir ₄ Cu ₄ (L-cys) ₁₂ ] and nH ₂ O were synthesized.

[Reference Example 6] K ₆ [Rh ₄ Hg ₄ (L-cys) ₁₂ O] ・_{Synthesis of nH 2} O In Example 1 of WO2019 / 208753, Hg (ClO ₄ ) ₂ was used _{instead of ZnBr 2.} except that performs the same operation as in example 1 of WO WO2019 / _208753, was synthesized _{K 6 [Rh 4 Hg 4 (} L-cys) 12 O] · nH 2 O.

When the compounds obtained in Reference Examples 1 to 6 were subjected to fluorescent X-ray analysis and single crystal X-ray crystal structure analysis, these compounds contained components of ionic flow type ionic solids (1) to (3). It was confirmed that an anionic polynuclear metal complex having the same structure as that of the above was contained.
Also, exchangeable cation species were present in the space between these anionic polynuclear metal complexes.
In addition, the space between these anionic polynuclear metal complexes was large enough to form cubane-containing clusters.
Therefore, in the same method as in Examples 1 to 24, by using the compounds obtained in Reference Examples 1 to 6 instead of the ionic flow type ionic solids (1) to (3), in Reference Examples 1 to 6. Efficiently synthesizes the metal-organic structure of the present invention having a cluster (α) derived from the obtained compound and a cluster (β) containing a cubane-type structure containing _{a metal ion (M β ion) as an essential component.} can.

Claims (15)

1. A metal-organic framework containing clusters (α) and clusters (β) as constituent units, respectively.
   The cluster (α) contains _{a metal ion (M α} ion) and a ligand (ligand L _{α ) coordinated to the M α ion.}
   The cluster (β) contains a cubane-type structure containing _{a metal ion (M β ion) as an essential component.}
   At least one ligand L _alpha is a polydentate ligand coordinating to M _beta ions (ligand L _alpha ^1), metal organic structures.
2. The cluster (α) is the M _α ion.
   _{A divalent or trivalent metal ion (M α} ¹ ion) capable of forming a complex having an octahedral molecular structure with a coordination number of 6 and
   Capable of forming a complex with a tetrahedral molecular structure of the coordination number of 4, a monovalent or divalent metal ion (M _alpha ² ions),
   The metal-organic framework according to claim 1.
3. The M _α ¹ ion is an ion of one kind of metal selected from the group consisting of the metals, Cr, and Mn of the 8th, 9th, and 10th groups of the periodic table.
   The metal-organic framework according to claim 2, wherein the M _α ² ion is an ion of one kind of metal selected from the group consisting of the metals of Group 11 and Group 12 of the Periodic Table.
4. The metal-organic structure according to any one of claims 1 to 3, wherein the ligand L _α ^{1 is represented by the following formula (1).}
   

   

   Wherein (1), ^{T 1} represents a first atom (ligand atoms ^{t 1)} or a group containing a coordination atom ^{t 1} coordinating to M _alpha ion, ^{T 2} is coordinated to M _alpha ion Represents a group containing a ^second atom (coordinating atom t ² ) or a coordinating atom t ^{2, where T 3} is an _{atom coordinating to an M β} ion (coordinating atom t ³ ) or a coordinating atom t ³ . Represents a group containing, and G represents a linking group. T ^1- GT ² is an atomic group that forms a 5-membered chelate ring or a 6-membered chelate ring by coordinating the coordination atom t ¹ and the coordination atom t ² to the M _{α ion.}
5. The metal-organic framework according to any one of claims 1 to 4, wherein the ligand L _α ^{1 is an amino acid.}
6. The metal-organic structure according to any one of claims 1 to 5, wherein the cluster (α) is represented by the following formula (2).
   

   

   In formula (2), M _α ¹ represents a divalent or trivalent metal ion capable of forming a complex having an octahedral molecular structure having a coordination number of 6, and M _α ² is a tetrahedron having a coordination number of 4. Represents a monovalent or divalent metal ion capable of forming a complex of body type molecular structure, L _α ¹ represents a polydentate ligand that also coordinates with M _β ^{ion, and E represents H −} , O ^{2 -, S 2-, Se 2-,} Te 2-, F -, Cl -, Br - or I ^- it represents a. m is 0 or 1, and n is ( _{valence of M α} ¹ × 4) + ( _{valence of M α} ² × 4) + ( _{valence of L α} ¹ × 12) + (valence of E). It is a number calculated by × m).
7. The aggregate of clusters (α) is derived from the anion part of the ionic flow type ionic solid.
   The ionic flow type ionic solid is formed by accumulating metal ions and an anionic polynuclear metal complex containing a polydentate ligand to form a crystal lattice, and cation species are present in the gaps of the crystal lattice. The metal organic structure according to any one of claims 1 to 6.
8. The metal-organic framework according to any one of claims 1 to 7, wherein the M _β ion is an ion of a d-block transition metal or an ion of an f-block transition metal.
9. The metal-organic framework according to any one of claims 1 to 8, wherein the M _{β ion satisfies the following requirements 1 and 2.}
   Requirement 1: A monovalent, divalent or trivalent metal ion capable of forming a complex having a polyhedral molecular structure having a coordination number of 4 or more.
   Requirement 2: The ionic radius is 70 to 120 pm.
10. The metal-organic structure according to any one of claims 1 to 9, wherein the cubane-type structure in the cluster (β) is a complete cubane-type structure with four nuclei or an incomplete cubane-type structure with three nuclei.
11. The metal-organic structure according to any one of claims 1 to 10, wherein the cubane-type structure in the cluster (β) further contains a hydroxide ion as a component.
12. The metal-organic structure according to any one of claims 1 to 11, wherein the cluster (β) is represented by the following formula (3).
    

    

    In formula (3), M _β represents a metal ion constituting a cubane-type structure, and L _β represents a carboxylate ligand. p is an integer of 0 to 10, q is an integer of 0 to 10 (where p + q ≧ 1), and r is ( _{valence of M β} × 4) + (-1 × 4) + (value of _{L β).} It is a number calculated by (number × q).
13. Ligand L _alpha ¹ is be one having a carboxylate group, coordinate bond between the ligand L _alpha ¹ carboxylate groups and M _beta ions are formed, according to claim 1 to 12 The metal-organic framework according to any one.
14. The metal-organic structure according to any one of claims 1 to 13, wherein the composition formula of the metal-organic structure is represented by the following formula (4).
    

    

    In formula (4), A represents a cation or anion. {(M _β ) ₄ (OH) ₄ (H ₂ O) _p (L _β ) _q } is an r-valent cation, M _β represents a metal ion constituting a cubane-type structure, and L _β is a carboxy. Represents a rate ligand. p is an integer of 0 to 10 and q is an integer of 0 to 10 (where p + q ≧ 1). {(M _α ¹ ) ₄ (M _α ² ) ₄ (L _α ¹ ) ₁₂ (E) _m } is an n-valent anion, and M _α ¹ is a complex having an octahedral molecular structure with a coordination number of 6. Representing a divalent or trivalent metal ion that can be formed, M _α ² represents a monovalent or divalent metal ion that can form a complex with a tetrahedral molecular structure having a coordination number of 4, L _α ^1. represents a coordinating polydentate ligand to M _beta ^{ion, E is, H -, O 2-, S} 2-, Se 2-, Te 2-, F -, Cl -, Br - or I ^- represents a. m is 0 or 1. B represents a solvent molecule, and t is an integer of 20 to 100. y and z are independently numbers greater than 0 and 1 or less, and x is a number satisfying (valence of A × x) + (r × y) − (n × z) = 0.
15. It is a method for manufacturing metal-organic frameworks.
    An ionic flow-type ionic solid in which metal ions and anionic polynuclear metal complexes containing polydentate ligands accumulate to form a crystal lattice and cation species are present in the gaps of the crystal lattice.
    A method for producing a metal-organic framework having a cubane-type structure in a metal-organic polymer chain, which comprises a step of contacting with a solution containing d-block transition metal ions or f-block transition metal ions.

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