WO2016143876A1

WO2016143876A1 - Ligand compound, and single-hole or multi-hole coordination polymer obtained using same

Info

Publication number: WO2016143876A1
Application number: PCT/JP2016/057669
Authority: WO
Inventors: 進北川; 亮太郎松田; 暢彦細野
Original assignee: 国立大学法人京都大学
Priority date: 2015-03-10
Filing date: 2016-03-10
Publication date: 2016-09-15
Also published as: JPWO2016143876A1

Abstract

Provided is a substance separation membrane (in particular, gas separation membrane) obtained using a ligand compound capable of producing the MOP. Also provided is a single-hole or multi-hole coordination polymer which comprises metal ions having a valence of 2 or greater and an organic ligand represented by general formula (3), the metal ions and the organic ligand have been alternately bonded by coordinate bonding. The coordination polymer can be formed into a film without requiring the use of a polymer matrix and can have solvent solubility and moldability. [In the formula, m is an integer of 1-3; X¹ represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group, or an optionally substituted heteroaromatic group; X² represents a single bond or a divalent linking group; R¹ represents a hydrogen atom or an optionally substituted alkyl group and when m is 2 or greater, then the R¹ moieties may be the same or different; R² represents a group represented by formula BB; Y represents an aromatic hydrocarbon ring or a heteroaromatic ring; the Z moieties may be the same or different and each represent an optionally substituted ethylene chain; and n is an integer of 5-20,000.]

Description

Ligand compound and monoporous or porous coordination polymer using the same

The present invention relates to a ligand compound and a monoporous or porous coordination polymer.

Organometallic polyhedra (Metal-Organic Polyhedra: MOP), which are complexed with organic ligands and metal ions and built in a self-organized manner, are cage-like compounds with voids of several to several nanometers inside. There is (for example, Non-Patent Document 1). MOP can incorporate various small molecules inside the cage structure, and not only as a supramolecular host, but also in recent years as an adsorption and / or separation material for substances such as gases using its pores. Widely studied (for example, Non-Patent Document 2). However, a simple MOP is usually obtained as a crystal or powdered solid, is hardly soluble in various solvents, and does not melt even when heated. Therefore, it has poor molding processability such as solution coating and thermoforming, which are indispensable for widespread use as a general-purpose material.

As described above, although MOP has poor molding processability, various methods for forming a film have been attempted in order to utilize its unique structure (for example, Non-Patent Document 3). However, any of these methods is a method for forming a film by dispersing MOP in a polymer matrix, and there is no method for forming a film of MOP without using a polymer matrix.

As mentioned above, since MOP has its unique structure, application to various uses is attempted, but it can be treated only as a powdery microcrystalline solid for the purpose of adsorption and / or separation of substances, Further, it is poor in solvent solubility and molding processability, so that it can be formed into a film only by a method of dispersing in a polymer matrix. On the other hand, in order to popularize MOP as a general-purpose material, a material that can be processed by a general-purpose process such as thermoforming and coating is preferable. In addition, in the filming method in which MOP is dispersed in the polymer matrix, the MOP content in the film can be increased to about 40-50% by mass, but there is no bond between MOP and the polymer matrix, There is a problem that the strength of the film is significantly reduced. Therefore, the present invention designs a compound in which MOP and a polymer are chemically bonded, MOP that can be formed into a film without using a polymer matrix, imparted solvent solubility and thermoforming processability, and It aims at providing the ligand compound which can manufacture the said MOP. The present invention also provides a material separation membrane (especially a gas separation membrane) using MOP that has been provided with solvent solubility and thermoforming processability by chemically bonding MOP and polymer in this way. Also aimed.

As a result of intensive studies in view of the above problems, the present inventors have conducted reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) of a desired polymer compound from the outer surface of the MOP, while maintaining the characteristics of the MOP, It has been found that high solvent solubility derived from a polymer compound, molding processability, and the like can be imparted. The MOP to which such solvent solubility and moldability are imparted is formed by a specific metal ion and a specific organic ligand being alternately coordinated. Based on such knowledge, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

Item 1. General formula (1):

[Wherein, m represents an integer of 1 to 3. X ¹ represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group. X ² represents a single bond or a divalent linking group. R ¹ represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R ¹ may be the same or different. R ² is

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. ]
A ligand compound represented by:

Item 2. R ² is

Item 2. The ligand compound according to Item 1, which is a group represented by:

Item 3. X ² represents the general formula (2):

[Wherein R ³ represents a hydrogen atom or an optionally substituted alkyl group. R ⁴ represents a hydrogen atom, an optionally substituted alkyl group or a cyano group. X ³ represents a single bond, an optionally substituted alkylene group, or a group represented by —R ⁵ —COO— (R ⁵ represents an optionally substituted alkylene group). ]
Item 3. The ligand compound according to

Item

1 or 2, which is a group represented by:

Item 4. Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring. Yes,
Said monocyclic or condensed and COO ^- in the binding of the group, the general formula (6):

[Wherein R ⁸ is the same or different and represents a carbon atom or a nitrogen atom. R ⁹ represents a divalent aromatic hydrocarbon group which may be substituted. k represents an integer of 0-2. ]
Item 4. The ligand compound according to any one of Items 1 to 3, which may contain a group represented by:

Item 5. Metal ions having a valence of 2 or more and general formula (3):

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. Z is the same or different and represents an optionally substituted ethylene chain. n represents an integer of 5 to 20000. ]
A monoporous or porous coordination polymer comprising an organic ligand represented by the formula (1) and wherein the metal ion and the organic ligand are alternately coordinated.

Item 6. R ² is

Item 6. A monoporous or porous coordination polymer according to Item 5, which is a group represented by:

Item 7. X ² represents the general formula (2):

[Wherein R ³ represents a hydrogen atom or an optionally substituted alkyl group. R ⁴ represents a hydrogen atom, an optionally substituted alkyl group or a cyano group. X ³ represents a single bond, an optionally substituted alkylene group, or a group represented by —R ⁵ —COO— (R ⁵ represents an optionally substituted alkylene group). ]
Item 7. The monoporous or porous coordination polymer according to

Item

5 or 6, which is a group represented by:

Item 8. Said Z is the general formula (4):

[Wherein R ⁶ represents a hydrogen atom or an optionally substituted alkyl group. R ⁷ is a hydroxyl group, an optionally substituted carboxy group, an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl Indicates a group. ]
Item 8. The monoporous or porous coordination polymer according to any one of Items 5 to 7, which is a chain represented by:

Item 9. Item 9. A monoporous or porous coordination polymer according to any one of Items 5 to 8, comprising the metal ion and the organic ligand.

Item 10. Item 10. The monoporous or porous coordination polymer according to any one of Items 5 to 9, which contains 4 or more metal ions and 4 or more organic ligands.

Item 11. Item 11. The monoporous or porous coordination polymer according to any one of Items 5 to 10, wherein the metal ion is a divalent metal ion.

Item 12. Item 12. The monoporous or porous coordination polymer according to any one of Items 5 to 11, wherein the metal ion is a transition metal ion.

Item 13. The metal ion is at least one selected from the group consisting of copper ion, zinc ion, cobalt ion, cadmium ion, rhodium ion, calcium ion, magnesium ion, manganese ion, nickel ion, palladium ion, lanthanum ion, and zirconium ion. Item 15. The monoporous or porous coordination polymer according to any one of Items 5 to 12, wherein

Item 14. Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring. Yes,
Said monocyclic or condensed and COO ^- in the binding of the group, the general formula (6):

[Wherein R ⁸ is the same or different and represents a carbon atom or a nitrogen atom. R ⁹ represents a divalent aromatic hydrocarbon group which may be substituted. k represents an integer of 0-2. ]
Item 14. The monoporous or porous coordination polymer according to any one of Items 5 to 13, which may contain a group represented by:

Item 15. Item 15. The monoporous or porous coordination polymer according to any one of Items 5 to 14, which is an organometallic polyhedron.

Item 16. Item 16. The monoporous or porous coordination polymer according to Item 15, having an average diameter of 2 nm to 100 nm.

Item 17. Item 17. The monoporous or porous coordination polymer according to

Item

15 or 16, which has one pore having an average diameter of 2 nm or less inside.

Item 18. A method for producing an organometallic polyhedron having polymer chains introduced therein,
Using an organometallic polyhedron and a monomer compound, and a step of performing reversible addition-fragmentation chain transfer polymerization,
The organometallic polyhedron has a divalent or higher valent metal ion and a general formula (5):

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. ]
And a metal ion and the organic ligand are alternately coordinate-bonded to each other.

Item 19. Item 18. A material for adsorbing and / or separating a substance comprising a monoporous or porous coordination polymer according to any one of Items 5 to 17.

Item 20. Item 20. The material for adsorbing and / or separating a substance according to Item 19, which is at least one member selected from the group consisting of a gas and / or ion adsorbing material and a gas and / or ion separating material.

Item 21. Item 18. A substance separation membrane comprising the monoporous or porous coordination polymer according to any one of Items 5 to 17, or the substance adsorption and / or separation material according to Item 19 or 20.

Item 22. Item 22. The substance separation membrane according to Item 21, which is a gas and / or ion separation membrane.

By using the ligand compound of the present invention, a polymer chain can be easily introduced into a monoporous or porous coordination polymer. This ligand compound is a novel compound not described in any literature.

The monoporous or porous coordination polymer of the present invention thus produced has high solvent solubility and molding processing derived from the polymer while maintaining the properties of the original monoporous or porous coordination compound. Therefore, it is possible to expand the applicability to existing mass production molding processes.

6 is a photograph showing the appearance of a substance separation membrane obtained in Example 6. 4 is a graph showing the results of GPC measurement of the compounds obtained in Synthesis Examples 1 to 3. 3 is a graph showing the results of GPC measurement of the compounds obtained in Examples 1 to 5 and Synthesis Examples 4 to 8. 6 is a graph showing the results of GPC measurement and reaction rate of the compounds obtained in Synthesis Examples 4 to 8. It is an electron micrograph which shows the surface structure of the substance separation membrane obtained in Example 7 and 8 (Example 7: Transmission electron microscope (TEM), Example 8: Atomic force microscope (AFM)). 6 is a graph showing the results of nitrogen and carbon dioxide adsorption / desorption tests of MOP1 obtained in Synthesis Example 2. FIG. 6 is a graph showing the results of GPC measurement of the compounds obtained in Examples 9 to 10 and Synthesis Examples 8 to 9. 4 is a graph showing the measurement results of the diameters of the compounds obtained in Synthesis Example 2, Example 1 and Example 8. 3 is a graph showing the results of GPC measurement of the compounds obtained in Examples 11 to 15 and Synthesis Examples 18 to 23. (A) is a plot of polymerization reaction time and monomer conversion, (b) is a plot of monomer conversion and MOP number average molecular weight (●: number average molecular weight, ■: molecular weight dispersion (Mw / Mn)), (c) is 2 is a graph showing a plot of monomer conversion and number average molecular weight of decomposed organic ligand (●: number average molecular weight, ■: molecular weight dispersion (Mw / Mn)).

1． Ligand Compound The ligand compound of the present invention has the general formula (1):

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. ]
(Hereinafter also referred to as “ligand compound (1)”).

The ligand compound (1) is obtained from the viewpoint of obtaining a monoporous or porous coordination polymer having a three-dimensional framework structure by connecting metal ions and clusters thereof by the production method described later. It has a plurality (two) of carboxy groups capable of coordinating with metal ions. When there is only one carboxy group, a three-dimensional framework structure cannot be constructed, and a monoporous or porous coordination polymer cannot be obtained.

Further, the ligand compound (1) has a dithioester structure that can be the starting point of reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) employed in the production method described later. When a monoporous or porous coordination polymer is produced using such a ligand compound (1), a polymer chain derived from the polymer compound (an ethylene chain which may be substituted) is converted to a single molecule such as MOP. It becomes possible to introduce into the organic ligand constituting the porous or porous coordination compound, and the solvent solubility, molding processability, etc. of the polymer compound can be changed to a monoporous or porous coordination compound such as MOP. Can be granted.

In the general formula (1), examples of the aromatic hydrocarbon group represented by X ¹ include a benzene ring, a pentalene ring, an indene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, a perylene ring, and triphenylene. And groups derived from aromatic hydrocarbon rings such as a ring, an azulene ring, a heptalene ring, a biphenylene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring and a phenanthrene ring. These groups derived from aromatic hydrocarbon rings include, for example, 0 to 4 substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (methyl groups, ethyl groups, propyl groups, etc.). It can also have about 1 (particularly 1 to 3).

In the general formula (1), examples of the heteroaromatic group represented by X ¹ include a furan ring, a thiophene ring, a pyrrole ring, a silole ring, a borol ring, a phosphole ring, an oxazole ring, a thiazole ring, a pyridine ring, and a pyridazine ring. , Groups derived from heteroaromatic rings such as pyrimidine ring, pyrazine ring, thienothiophene ring and quinoline ring. In these heteroaromatic ring-derived groups, for example, 0 to 4 substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (methyl groups, ethyl groups, propyl groups, etc.) ( In particular, it may have about 1 to 3).

X ¹ in the general formula (1) is various in the monoporous or porous coordination polymer of the present invention in order to give easy synthesis and good living radical polymerization reactivity to various monomers in the production method described later. From the viewpoint of giving such characteristics, a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group, and the like are preferable, and a sulfur atom is more preferable.

In the general formula (1), examples of the divalent linking group represented by X ² include the general formula (2):

[Wherein, R ³ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R ⁴ represents a hydrogen atom, an optionally substituted alkyl group, a cyano group, or an optionally substituted aryl group. X ³ represents a single bond, an optionally substituted alkylene group, or a group represented by —R ⁵ —COO— (R ⁵ represents an optionally substituted alkylene group). ]
The group etc. which are represented by these are mentioned.

In the general formula (2), examples of the alkyl group represented by R ³ include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).

In the general formula (2), examples of the aryl group represented by R ³ include a phenyl group and a naphthyl group. These aryl groups may have about 0 to 5 (especially 1 to 3) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.) and the above alkyl groups.

R ³ in the general formula (2) is preferably an alkyl group which may be substituted, from the viewpoint of easy synthesis and good living radical polymerization reactivity for various monomers in the production method described later. The methyl group which may be sufficient is more preferable, and a methyl group (unsubstituted) is further more preferable.

In the general formula (2), examples of the alkyl group represented by R ⁴ include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).

In the general formula (2), as the aryl group represented by R ⁴ , those described above can be adopted. The kind and number of substituents are the same.

R ⁴ in the general formula (2) is preferably a cyano group or an optionally substituted aryl group from the viewpoint of ease of synthesis and good living radical polymerization reactivity for various monomers in the production method described below. A cyano group is more preferable.

In the general formula (2), examples of the alkylene group represented by X ³ include methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, propylidene group, tetramethylene group, 1-methyltrimethylene group, 2- Acyclic alkylene group such as methyltrimethylene group, 3-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group (preferably having 1 to 6 carbon atoms, particularly having 1 to 4 carbon atoms) Acyclic alkylene group); cyclic alkylene group such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, etc. (preferably a cyclic alkylene group having 3 to 10 carbon atoms, especially 3 to 8 carbon atoms) Etc. In addition, when employ | adopting an acyclic alkylene group, a linear acyclic alkylene group can also be employ | adopted and a branched acyclic alkylene group can also be employ | adopted. These alkylene groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.).

X ³ in the general formula (2) is an ester group in which these alkylene groups are linked (the group represented by the above -R ⁵ -COO- (R ⁵ represents an optionally substituted alkylene group)). For example, —CH ₂ COO— group, —CH ₂ CH ₂ COO— group, —CH (CH ₃ ) COO— group, —CH ₂ CH ₂ CH ₂ COO— group, —CH (CH ₃ ) CH ₂ COO— group, —CH (CH ₂ CH ₃ ) COO— group, —CH ₂ CH ₂ CH ₂ CH ₂ COO— group, —CH (CH ₃ ) CH ₂ CH ₂ COO— group, —CH ₂ CH (CH ₃ ) CH ₂ COO— group, —CH ₂ CH ₂ CH (CH ₃ ) COO— group, —CH (CH ₃ ) ₂ CH ₂ COO— group, —CH (CH ₃ ) CH (CH ₃ ) CH ₂ COO— group, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ COO— group and the like can be mentioned.

X ³ in the general formula (2) is an ester group in which an alkylene group is linked from the viewpoint of ease of synthesis (the above -R ⁵ -COO- (wherein R ⁵ represents an optionally substituted alkylene group)). Are preferred.

In the general formula (1), the alkyl group represented by R ¹ is not particularly limited, and any of a straight chain alkyl group and a branched chain alkyl group may be employed. From the viewpoint of further improving the solvent solubility mainly in a nonpolar solvent, a linear alkyl group is preferable for the compound. The number of carbon atoms of such an alkyl group is preferably 1 to 100 from the viewpoint of further improving the solubility of the monoporous or porous coordination compound such as MOP mainly in a nonpolar solvent. 20 is more preferable, and 8 to 16 is more preferable. Specific examples of such an alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. These alkyl groups can also have about 0 to 10 (especially 1 to 5) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.). In the general formula (1), when m which is the number of R ¹ is 2 or more, R ¹ may be the same or different.

R ¹ in the general formula (1) is preferably an alkyl group which may be substituted from the viewpoint of ease of synthesis and good living radical polymerization reactivity with respect to various monomers in the production method described later. Groups are more preferred.

In the general formula (1), m, which is the number of R ¹ , is a number determined by the type of X ¹ , valence, etc., and is an integer of 1 to 3, preferably 1 or 2.

In the general formula (1), R ² represents a dithioester structure,

The group represented by these is shown.

By having such a structure, it can be the starting point of reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) in the production method described later. As such R ² , from the viewpoint of easy synthesis and good living radical polymerization reactivity for various monomers in the production method described below,

The group represented by these is preferable.

In the case of producing an organometallic polyhedron (monoporous coordination polymer) using the ligand compound of the present invention, the ligand compound (1) and a metal ion described later are coordinated alternately. In order to form a spherical polymer compound having micropores inside by forming a bond, the angle formed by two Y—COO ^— bonds is preferably less than 180 °. In the ligand compound (1), if the angle between the two Y—COO ^— bonds is less than 180 °, the angle between the two Y—COO ^— bonds can be used, Spherical monoporous or porous coordination polymers can be produced. As this spherical compound, an organometallic polyhedron (monoporous coordination polymer) having micropores inside can be produced.

As Y satisfying such conditions, an aromatic hydrocarbon ring which may have a hetero atom is preferred, and a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, thiophene ring, etc., or one in these rings or two or more benzene rings include condensed rings, etc. these rings and COO ^- in the binding of the group, the general formula (6):

[Wherein R ⁸ is the same or different and represents a carbon atom or a nitrogen atom. R ⁹ represents a divalent aromatic hydrocarbon group which may be substituted. k represents an integer of 0-2. ]
The group represented by may be included.

In the general formula (6), as the divalent aromatic hydrocarbon group represented by R ⁹ , those described above can be adopted. The kind and number of substituents are the same. In general formula (6), k is preferably an integer of 0 to 2, more preferably 0 or 1.

Among them, Y is preferably a benzene ring, a naphthalene ring, a pyridine ring, a pyrrole ring, a thiophene ring, or the like, or a ring in which one or two or more benzene rings are condensed to these rings, a benzene ring, a naphthalene ring, A pyridine ring, a pyrrole ring, a thiophene ring and the like are more preferable, and a benzene ring is more preferable.

Such Y is, for example,

Etc.

Such a ligand compound (1) can be obtained by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) for coordination with metal ions by the production method described later. Can give. In particular, it is possible to produce a porous coordination polymer having a jungle gym-like three-dimensional framework structure, and it is also possible to confine a large number of compounds inside.

Examples of ligand compounds (1) that satisfy these conditions include:

From the viewpoint of giving good living radical polymerization reactivity to various monomers in the production method described below,

Etc. are preferred.

2． Monoporous or Porous Coordination Polymer The monoporous or porous coordination polymer of the present invention comprises a divalent or higher valent metal ion and a general formula (3):

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. Z is the same or different and represents an optionally substituted ethylene chain. n represents an integer of 5 to 20000. ]
And the metal ion and the organic ligand are alternately coordinated and bonded to each other (hereinafter also referred to as “organic ligand (3)”). ing.

As the divalent or higher-valent metal ion constituting the monoporous or porous coordination polymer of the present invention, a transition metal ion can be preferably used, but it must be coordinated with the organic ligand (3). From the viewpoint of easily constituting a monoporous or porous coordination polymer, a divalent metal ion (particularly a divalent transition metal ion) is preferable. Specifically, copper ion, zinc ion, cobalt ion, cadmium ion, rhodium ion, calcium ion, magnesium ion, manganese ion, nickel ion, palladium ion, lanthanum ion, zirconium ion, etc. are preferable, and copper ion and zinc ion are preferred. More preferred. The metal ion is preferably used alone from the viewpoint of easy formation of a monoporous or porous coordination polymer by coordination bond with the organic ligand (3), but it should be used in combination of two or more. You can also.

The monoporous or porous coordination polymer of the present invention contains an organic ligand (3).

The organic ligand (3) is coordinated with the metal ion from the viewpoint of obtaining a monoporous or porous coordination polymer having a three-dimensional framework structure by linking the metal ion and its cluster. It has a plurality (two) of carboxy groups. When there is only one carboxy group, a three-dimensional framework structure cannot be constructed, and thus the monoporous or porous coordination polymer of the present invention cannot be obtained.

The organic ligand (3) has a dithioester structure that can be the starting point of reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) employed in the production method described later. By adopting such an organic ligand (3), a polymer chain derived from a polymer compound (an ethylene chain which may be substituted) constitutes a monoporous or porous coordination compound such as MOP. It can be introduced into the ligand, and the solvent solubility and molding processability of the polymer compound can be imparted to a monoporous or porous coordination compound such as MOP.

In the general formula (3), as the aromatic hydrocarbon group and heteroaromatic group represented by X ¹ , those described above can be adopted. The kind and number of substituents are the same. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, X ¹ in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

In the general formula (3), as the divalent linking group represented by X ² , those described above can be adopted. The kind and number of substituents are the same. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, X ² in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

In the general formula (3), as the alkyl group represented by R ¹ , those described above can be adopted. The kind and number of substituents are the same. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, R ¹ in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

As preferred examples of R ² , those described above can be employed. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, R ² in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

In the general formula (3), the above-mentioned thing can be adopted as m. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, m in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

In the general formula (3), as the aromatic hydrocarbon group and heteroaromatic group represented by Y, those described above can be adopted. The kind and number of substituents are the same. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, Y in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.

In the general formula (3), Z is an ethylene chain which may be substituted, and means a monomer unit of a polymerized polymer. More specifically, this optionally substituted ethylene chain (monomer unit of the polymerized polymer) is introduced into a monoporous or porous coordination compound such as MOP by RAFT polymerization in the production method described later. It is a structural unit derived from the monomer compound used in the process. That is, depending on the type of Z, various characteristics can be imparted to a monoporous or porous coordination compound such as MOP. As such Z, general formula (4):

[Wherein R ⁶ represents a hydrogen atom or an optionally substituted alkyl group. R ⁷ is a hydroxyl group, an optionally substituted carboxy group, an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl Indicates a group. ]
The chain represented by is preferred.

In the general formula (4), examples of the alkyl group represented by R ⁶ include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).

In general formula (4), R ⁶ maintains the characteristics of a monoporous or porous coordination compound such as MOP (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.) However, from the viewpoint of further improving solvent solubility and moldability (particularly thermoforming processability), an optionally substituted alkyl group is preferred, an unsubstituted alkyl group is more preferred, and a methyl group is more preferred.

In the general formula (4), the carboxy group represented by R ⁷ is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an n-hexyl group; an isobornyl group; a polyethylene glycol ( It can also have about 0 to 5 (especially 1 to 3) substituents such as (PEG) residues.

In the general formula (4), examples of the acyloxy group represented by R ⁷ include an acetoxy group, an ethanoyloxy group, a propionyloxy group, and the like, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. And an alkyl group such as an n-hexyl group; an isobornyl group; and a substituent such as a polyethylene glycol (PEG) residue may have about 0 to 5 (particularly 1 to 3) substituents.

In the general formula (4), the carbamoyl group represented by R ⁷ is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an n-hexyl group; an isobornyl group; a polyethylene glycol ( It can also have about 0 to 5 (especially 1 to 3) substituents such as (PEG) residues.

In the general formula (4), examples of the heteroaryl group represented by R ⁷ include a pyridyl group, a pyrrolyl group, a thienyl group, and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An alkyl group such as an n-hexyl group; an isobornyl group; and 0 to 5 (particularly 1 to 3) substituents such as a polyethylene glycol (PEG) residue may be included.

In the general formula (4), as the aryl group represented by R ⁷ , those described above can be adopted. The kind and number of substituents are the same.

In the general formula (4), R ⁷ maintains the characteristics of a monoporous or porous coordination compound such as MOP (having micropores inside, selectively absorbing carbon dioxide in the case of MOP). However, from the viewpoint of further improving solvent solubility and moldability (particularly thermoforming processability), an optionally substituted carboxy group or an optionally substituted aryl group is preferred, and the carboxy substituted with an alkyl group is preferred. A group or an unsubstituted aryl group is more preferable, and a carbonylmethoxy group or a phenyl group is more preferable.

Examples of Z satisfying such conditions include methacrylic acid or a derivative residue thereof (methyl methacrylate residue, n-butyl methacrylate residue, tert-butyl methacrylate residue, hexyl methacrylate residue, methacrylic acid residue). Isobornyl residue, methacrylic acid residue, methoxypolyethylene glycol (PEG) methacrylate), acrylic acid or its derivative residue (methyl acrylate residue, n-butyl acrylate residue, tert-butyl acrylate residue) Hexyl acrylate residue, isobornyl acrylate residue, acrylic acid residue, methoxypolyethylene glycol acrylate (PEG) residue, acrylamide residue, N-isopropylacrylamide residue), styrene or its derivative residue (styrene residue) Group, pentafluorostyrene residue), 4-vinylpyridine residue If a group derived from a polymer compound such as a polymethyl methacrylate resin, a polyacrylic acid resin, a polystyrene resin, a polyacrylamide resin, or a polyvinyl alcohol resin is introduced, such as a group, a vinyl acetate residue, a vinyl alcohol residue, Solvent solubility and moldability (especially heat) while maintaining the properties of monoporous or porous coordination compounds such as MOP (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.) Molding processability) can be improved. At this time, examples of the solvent that can improve the solvent solubility include toluene, chloroform, tetrahydrofuran, N, N′-dimethylformamide, dichloromethane, benzene, 1,4-dioxane, carbon tetrachloride, acetone, dichlorobenzene and the like. Is mentioned. In particular, it is useful in that it can be dissolved in a solvent having a low polarity such as toluene, chloroform, or benzene.

Also, polymethacrylic acid, polysodium methacrylate, polyacrylic acid, polyacrylic, such as methacrylic acid residue, acrylic acid residue, vinyl alcohol residue, methoxy acrylate acrylate residue, 4-vinylpyridine residue, etc. By introducing groups derived from water-soluble polymer compounds such as sodium acrylate, polyvinyl alcohol, methoxy PEG polyacrylate, and poly (4-vinylpyridine), the properties of monoporous or porous coordination compounds such as MOP (internal In the case of MOP, the water solubility can be improved while maintaining the selective absorption of carbon dioxide.

Among these, from the viewpoint of ease of synthesis and further improving solvent solubility, solution processability, and thermal processability in monoporous or porous coordination compounds such as MOP, Z is a methyl methacrylate residue. Or as a styrene residue,

Is preferably adopted.

As such Z, a single group may be employed, or two or more groups may be employed. For example, if an organic ligand (3) having two or more kinds of Z is employed, the properties possessed by two or more different polymer compounds may be imparted to a monoporous or porous coordination compound such as MOP. Is possible.

In the general formula (3), n, which is the number of repeating Z, is not particularly limited, and is a characteristic of a monoporous or porous coordination compound such as MOP (in the case of MOP, carbon dioxide in the case of MOP having micropores inside) From the viewpoint of further improving the molding processability (especially thermoforming processability) and imparting ion exchange ability, further improving the solvent solubility, and the like. An integer is preferable, and an integer of 10 to 500 is more preferable. The monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to align the length of each organic ligand (3). . Specifically, it is possible to narrow the dispersion of n in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention.

On the other hand, such an organic ligand (3) can give a porous coordination polymer by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) when coordinated with a metal ion. In particular, a porous coordination polymer having a jungle gym-like three-dimensional framework structure can be used, and a large number of compounds can be confined inside.

Such an organic ligand (3) is not particularly limited, and specifically includes a general formula:

[Wherein n is the same as defined above. ]
From the viewpoint of giving good living radical polymerization reactivity to various monomers,

Etc. are more preferable.

The number of metal ions possessed by the monoporous or porous coordination polymer of the present invention is the type of metal ion, the angle between two Y-COO ^- bonds, the monoporous or porous coordination of the present invention. Depending on the average diameter of the polymer, etc., it is preferably 4 to 128, more preferably 12 to 48, and particularly preferably 24. In addition, the number of organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention depends on the type of metal ion, the angle formed by two Y—COO ^— bonds, Depending on the average diameter of the porous or porous coordination polymer, etc., it is preferably 4 to 128, more preferably 12 to 48, and particularly preferably 24. When copper ions (Cu ²⁺ ) are used as metal ions and organic ligands (Y) are organic ligands where Y is a benzene ring, copper ions (Cu ²⁺ ) and organic Organometallic polyhedra (monoporous coordination polymers) each having 24 ligands are easily generated.

In single-hole or porous coordination polymer of the present invention, Y (aromatic hydrocarbon ring or heteroaromatic ring) two COO bound to ^- group, coordinated to two or more valent metal ions It is a group to do. That is, the monoporous or porous coordination polymer of the present invention has a configuration in which the divalent or higher-valent metal ion and the organic ligand (3) are alternately coordinated. . At this time, the monoporous or porous coordination polymer of the present invention may contain ions or ligands other than the divalent or higher metal ion and the organic ligand (3), From the viewpoint of ease of synthesis and analysis, and from the viewpoint of stably presenting a monoporous or porous coordination compound such as MOP, the monoporous or porous coordination polymer of the present invention comprises the above-described divalent or higher-valent metal ions and It is preferable to consist only of the organic ligand (3).

In the organic ligand (3), if the angle formed by the two Y—COO ^— bonds is less than 180 °, the angle formed by the two Y—COO ^— bonds is used. The monoporous or porous coordination polymer of the present invention can be a spherical compound. This spherical compound can be an organometallic polyhedron (monoporous coordination polymer) having micropores inside.

When the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron (monoporous coordination polymer), the average diameter is not particularly limited, but it may be a monoporous or porous coordination such as MOP. From the viewpoint of imparting ion exchange capacity and further improving solvent solubility, while maintaining the properties of the coordination compound (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.) 3 to 100 nm is preferable, and 5 to 50 nm is more preferable.

When the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron (monoporous coordination polymer), the average diameter of the pores present in the interior is not particularly limited, but a single unit such as MOP can be used. From the viewpoint of maintaining the characteristics of the porous or porous coordination compound (having micropores inside, in the case of MOP, selectively absorbing carbon dioxide, etc.), it is preferably 2 nm or less, preferably 0.1 to 1.5 nm. More preferred.

When the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron (monoporous coordination polymer), the average molecular weight is not particularly limited, but it may be a monoporous or porous coordination such as MOP. From the viewpoint of imparting ion exchange capacity and further improving solvent solubility, while maintaining the properties of the coordination compound (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.) The number average molecular weight is preferably 5000-2000000, and more preferably 7000-200000.

On the other hand, in the organic ligand (3), a porous coordination polymer can be provided by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) for coordination with metal ions. In particular, a porous coordination polymer having a jungle gym-like three-dimensional framework structure can be used, and a large number of compounds can be confined inside.

3． Production Method of Monoporous or Porous Coordination Polymer The production method of the monoporous or porous coordination polymer of the present invention is not particularly limited, and can be synthesized by various methods. For example, when synthesizing an organometallic polyhedron (monoporous coordination polymer) as the monoporous or porous coordination polymer of the present invention, for example, reaction formula 1:

[Wherein, X ¹ , X ² , R ¹ , R ² , Y and m are the same as defined above. ]
Can be synthesized according to

(2-1) Ligand compound (1)
The ligand compound (1) in the above reaction formula 1 is the above-described ligand compound of the present invention.

In the ligand compound (1), for example, X ² is a group represented by the above general formula (2) as a divalent linking group, and X ³ is —R ⁵ —COO— (where R ⁵ is substituted). In an organic solvent, the general formula (7):

[Wherein, X ¹ , X ³ , R ¹ , R ² , R ³ , R ⁴ and m are the same as defined above. ]
And a compound represented by the general formula (8):

[Wherein Y is the same as defined above. ]
It can obtain by making it react with the compound (henceforth "compound (8)") represented by these.

In this case, since the compound (7) is easily hydrolyzed and very weak against acids and bases, the carboxy group is protected with a protecting group such as a silyl group (such as t-butyldimethylsilyl group), and the compound (8 ), And then esterification, preferably under neutral conditions, by known methods (eg, adding oxalyl chloride and a catalytic amount of N, N′-dimethylformamide to produce acid chloride in the reaction system). Preferably it is done.

The amount of the compound (7) used is not particularly limited, but from the viewpoint of yield and the like, it is preferable to use 0.2 to 1 mol (particularly 0.5 to 0.9 mol) with respect to 1 mol of the compound (8).

In addition, when protecting and deprotecting the compound (7), a base such as pyridine and amines (trimethylamine, N, N′-diisopropylethylamine, etc.) may be added to accelerate the reaction.

As the organic solvent that can be used in this step, known ones may be employed. In this step, for example, cyclic ethers such as tetrahydrofuran and dioxane; halogen solvents such as dichloromethane and chloroform are preferable. These solvents are preferably strictly dehydrated. The reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, -20 to 100 ° C., particularly 0 to 50 ° C., 1 to 48 hours, particularly 2 to 24 hours. After completion of the reaction, usual isolation and purification steps can be performed as necessary.

The ligand compound (1) has, for example, R ²

In the case of a ligand compound represented by general formula (9):

[Wherein, X ¹ , R ¹ and m are the same as defined above. M represents a cation. ]
And a compound represented by the following general formula (10):

[Wherein X ² and Y are the same as defined above. X ⁴ represents a halogen atom. ]
It can obtain by making it react with the compound (henceforth "compound (10)") represented by these.

In the general formula (9), the cation represented by M is preferably an alkali metal cation, and examples thereof include a sodium cation and a potassium cation.

In the general formula (9), examples of the halogen atom represented by X ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In this case, since the compound (10) is easily hydrolyzed and very weak against acids and bases, the carboxy group is protected with a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group. Then, after adding the compound (9), the reaction is preferably carried out under neutral conditions by a known method (for example, a method of adding trifluoroacetic acid to form an ester in the reaction system).

The amount of compound (9) used is not particularly limited, but from the viewpoint of yield and the like, it is preferable to use 0.2 to 2 mol (particularly 0.5 to 1.5 mol) with respect to 1 mol of compound (10).

The organic solvent that can be used in this step may be a known one. In this step, for example, cyclic ethers such as tetrahydrofuran and dioxane; halogen solvents such as dichloromethane and chloroform; ketones such as acetone and methyl ethyl ketone; preferable. The reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, -20 to 100 ° C., particularly 0 to 50 ° C., 1 to 48 hours, particularly 2 to 24 hours. After completion of the reaction, usual isolation and purification steps can be performed as necessary.

R ² is

The ligand compound, which is a group represented by the formula (1), can also be produced according to the above method (by changing the raw materials or the like to a desired one).

In addition, the ligand compound (1) has, for example, X ¹ -R ²

In the case of a ligand compound represented by general formula (11):

[Wherein, R ¹ and m are the same as defined above. ]
Can be obtained by reacting CS ₂ with the above compound (10) (hereinafter also referred to as “compound (11)”).

In this case, since the compound (10) is easily hydrolyzed and very weak against acids and bases, the carboxy group is protected with a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group. Then, after adding the compound (11) and CS ₂ , the reaction is preferably carried out under neutral conditions by a known method (for example, a method of adding trifluoroacetic acid to form an ester in the reaction system).

The amount of the compound (11) and CS ₂ used is not particularly limited, but from the viewpoint of further improving the yield and further suppressing the production of by-products, 1 mol of the compound (10), Compound (11) is preferably used in an amount of 0.2 to 2 mol (particularly 0.5 to 1.5 mol), and CS ₂ is preferably used in an amount of 0.2 to 2 mol (particularly 0.5 to 1.5 mol).

(2-2) MOP-forming reaction In this step, an organometallic polyhedron (MOP) can be obtained by reacting the ligand compound (1) in the above reaction formula 1 with a metal compound in an organic solvent. it can.

The metal compound is not particularly limited, but a divalent metal salt is preferable from the viewpoint of easily configuring MOP. Although the metal species constituting such a divalent metal salt is not particularly limited, from the viewpoint of easily forming a monoporous or porous coordination polymer by coordination bond with the organic ligand (3), Transition metals such as copper, zinc, cobalt, cadmium, rhodium, calcium, magnesium, manganese, nickel, palladium, lanthanum, and zirconium are preferable, and copper or zinc is more preferable. In addition, as these metal salts, organic acid salts such as acetates and formates; inorganic acid salts such as sulfates, nitrates, carbonates, hydrochlorides, and hydrobromides can be used.

Specific examples of such metal compounds include copper (II) acetate, copper (II) nitrate, copper (II) chloride, zinc nitrate, cobalt (II) nitrate, cadmium acetate, and nickel (II) chloride. It can be preferably used. The metal compound may be a hydrate or a solvate. In addition, the metal compound is preferably used alone from the viewpoint of easy synthesis and structural analysis and from the viewpoint of easy formation of a stable MOP, but may be used in combination of two or more.

The amount of the metal compound used is preferably 0.5 to 2.0 moles per mole of the ligand compound (1).

As the organic solvent that can be used in this step, a known solvent may be employed. In this step, for example, amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone are preferable. The reaction conditions are not limited as long as the reaction proceeds sufficiently, and can be, for example, −50 to 100 ° C., particularly 10 to 40 ° C., 10 minutes to 24 hours, particularly 30 minutes to 12 hours. After completion of the reaction, it may be purified by precipitation in an alcohol solvent such as methanol, if necessary.

MOP obtained in this way is divalent or higher metal ion and general formula (12):

[Wherein, X ¹ , X ² , R ¹ , R ² , Y and m are the same as defined above. ]
And the metal ion and the organic ligand are alternately coordinated. That is, it is MOP in which a polymer chain is not introduced, and the description of the above “monoporous or porous coordination polymer” can be used for other characteristics.

(2-3) Polymerization reaction (RAFT polymerization)
In this process, a polymer chain can be introduced into MOP by causing RAFT polymerization using a desired monomer compound according to the required characteristics for MOP. Maintaining pores, selectively absorbing carbon dioxide, etc., while providing ion exchange capability, further improving solvent solubility, and further improving molding processability (especially thermoforming processability) Can do. Specifically, the compound of the present invention can be obtained by RAFT polymerization of MOP and a monomer compound in an organic solvent using a radical polymerization initiator.

Although it does not restrict | limit especially as a monomer compound, Solvent solubility and moldability (especially thermoforming processability) are maintained, maintaining the characteristic of MOP (it has a micropore inside, selectively absorbs carbon dioxide etc.). From the viewpoint of further improvement, the general formula (13):

[Wherein, R ⁶ and R ⁷ are the same as defined above. ]
In particular, methacrylic acid or a derivative thereof (methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, isobornyl methacrylate, methacrylic acid, methoxy methacrylate) is preferable. Polyethylene glycol (PEG)), acrylic acid or its derivatives (methyl acrylate, n-butyl acrylate, tert-butyl acrylate, hexyl acrylate, isobornyl acrylate, acrylic acid, methoxypolyethylene glycol acrylate (PEG), acrylamide N-isopropylacrylamide), styrene or its derivatives (styrene, pentafluorostyrene), 4-vinylpyridine, vinyl acetate, vinyl alcohol, and the like. Methyl methacrylate, methyl acrylate Acrylamide, styrene, vinyl acetate and the like are preferable. Examples of solvents that can improve solvent solubility include toluene, chloroform, tetrahydrofuran, N, N′-dimethylformamide, dichloromethane, benzene, 1,4-dioxane, carbon tetrachloride, acetone, dichlorobenzene, and the like. Can be mentioned. In particular, it is useful in that it can be dissolved in a solvent having a low polarity such as toluene, chloroform, or benzene.

In addition, if a water-soluble monomer compound such as methacrylic acid, acrylic acid, vinyl alcohol, methoxypolyethylene glycol acrylate (PEG), 4-vinylpyridine, etc. is used, the characteristics of MOP (with micropores inside, It is also possible to improve water solubility while maintaining (such as selectively absorbing carbon).

Of these, methyl methacrylate is particularly preferred from the viewpoint of ease of synthesis and imparting solvent solubility and thermoforming processability to MOP.

These monomer compounds can be used alone or in combination of two or more. In particular, if a plurality of monomer compounds are used, it is possible to introduce a copolymer polymer chain and impart characteristics derived from a plurality of different polymers.

The radical polymerization initiator is not particularly limited, and tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxyneodecanoate, peroxy Hydrogen peroxides such as tert-butyl isobutyrate, lauroyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate; 2,2'- Azobis (isobutyronitrile), 2,2'-azobis (2-butenonitrile), 4,4'-azobis (4-pentanoic acid), 1,1'-azobis (cyclohexanecarbonitrile), 2- (tert- Butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) ) -2-Hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl) propionamide, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dichloride, 2,2'-azobis (2-amidinopropane) chloride, 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1- Bis (hydroxymethyl) -2-hydroxyethyl] propionamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide), 2,2'-azobis Examples include azo compounds such as [2-methyl-N- (2-hydroxyethyl) propionamide] and 2,2′-azobis (isobutyrylamide) dihydrate.

The amount of the monomer compound and radical polymerization initiator used is not particularly limited. From the viewpoints of yield and molecular weight dispersion of the polymer obtained by RAFT polymerization, the ligand compound (1) residue 1 in MOP It is preferable to use 20 to 10000 mol (particularly 50 to 2000 mol) of the monomer compound and 0.01 to 2 mol (particularly 0.5 to 1 mol) of the radical polymerization initiator with respect to mol.

The organic solvent that can be used in this step may be a known one. In this step, for example, an aromatic solvent such as benzene, toluene, xylene, mesitylene, and anisole; a cyclic ether such as 1,4-dioxane Are preferred. The reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, 10 to 150 ° C., particularly 50 to 100 ° C., 10 minutes to 24 hours, particularly 30 minutes to 12 hours. After completion of the reaction, normal isolation and purification steps may be performed as necessary.

The completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by gas chromatography, high performance liquid chromatography or the like, but is not limited thereto. After completion of the reaction, the obtained mixed solution is put into a poor polymer solvent (especially an alcohol-based organic solvent such as methanol), subjected to suction filtration to collect a precipitate, washed with the poor solvent, and if necessary. The organometallic polyhedron (monoporous coordination polymer) of the present invention is vacuum-dried at a temperature at which the organometallic polyhedron (monoporous coordination polymer) does not decompose (for example, 25 to 250 ° C.) for several hours. ) Can be obtained. Cleaning with an organic solvent and vacuum drying can be replaced by cleaning with supercritical carbon dioxide, which is more effective.

This method can be applied to random copolymerization and block copolymerization of different monomers, and a monoporous or porous coordination polymer into which a copolymerized polymer chain is introduced can be obtained in the same manner. In the above, the method of introducing a polymer chain by RAFT polymerization was shown, but by other living polymerization (atom transfer radical polymerization (ATRP) method, nitroxide-mediated radical polymerization (NMP) method, anionic polymerization method, etc.)) It is also possible to introduce polymer chains. Although only the method for synthesizing the organometallic polyhedron (monoporous coordination polymer) has been described above, the porous coordination polymer can also be synthesized by the same method according to the above method.

Four. Substance Adsorption and / or Separation Material and Substance Separation Membrane The above-described monoporous or porous coordination polymer of the present invention is used as a substance adsorption and / or separation material by taking advantage of its unique substance absorption characteristics. be able to. In this case, the monoporous or porous coordination polymer of the present invention can adsorb and / or separate a substance in a gas state and can capture and / or separate a substance in an ionic state. Therefore, the monoporous or porous coordination polymer of the present invention can be preferably used as a gas and / or ion adsorbing material or a gas and / or ion separating material. Specifically, when the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron, a carbon dioxide adsorbing material or a carbon dioxide is utilized by utilizing the property of selectively adsorbing carbon dioxide. It can be suitably used as a separation material. Further, if a suitable design is applied to the monoporous or porous coordination polymer of the present invention, other gas species and ionic species can be similarly adsorbed and / or separated.

Before gas or the like is adsorbed in the pores of the monoporous or porous coordination polymer, a vacuum is used in order to remove moisture and solvent adsorbed on the monoporous or porous coordination polymer. Pre-drying is preferably performed.

Also, a film can be easily produced using the monoporous or porous coordination polymer of the present invention. Such a film can be used as a material separation membrane. In this case, the monoporous or porous coordination polymer of the present invention can adsorb and / or separate a substance in a gas state and can capture and / or separate a substance in an ionic state. For this reason, the substance separation membrane of the present invention can be a gas and / or ion separation membrane. Specifically, when the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron, it is suitably used as a carbon dioxide separation membrane by utilizing the property of selectively adsorbing carbon dioxide. can do. Further, if a suitable design is applied to the monoporous or porous coordination polymer of the present invention, other gas species and ionic species can be similarly adsorbed and / or separated.

Such a material separation membrane can be produced using, for example, a coating composition containing the monoporous or porous coordination polymer (material adsorption and / or separation material) of the present invention. As the coating composition, for example, a solution obtained by dissolving the monoporous or porous coordination polymer of the present invention in an organic solvent can be used. At this time, the monoporous or porous coordination polymer (substance adsorption and / or separation material) of the present invention can be used alone or in combination of two or more.

Examples of organic solvents that can be used include toluene, chloroform, tetrahydrofuran, benzene, N, N′-dimethylformamide, and the like.

At this time, the concentration of the monoporous or porous coordination polymer (substance adsorption and / or separation material) of the present invention is 1 to 100 mg / mL from the viewpoint of forming a more homogeneous and self-supporting film. 5 to 50 mg / mL is more preferable.

In the coating composition, a binder resin may be used. In the present invention, the monoporous or porous coordination polymer of the present invention (substance adsorption and / or separation) can be used without using a binder resin. In order to facilitate the development of the characteristics (material adsorption characteristics, substance separation characteristics, etc.) of the monoporous or porous coordination polymer of the present invention, the binder resin should not be used. preferable.

Furthermore, a leveling agent, a coupling agent, a thickener, an ultraviolet absorber, a light stabilizer, an antifreezing agent, and the like may be added to the coating composition as long as the effects of the present invention are not adversely affected. However, it is preferably not used for the same reason as described above.

The substance separation membrane of the present invention can be coated on a substrate by, for example, coating or spraying. The coating method is not particularly limited. For example, drop casting method, spin coating method, dip coating method, flow coating method, spray coating method, roll coating method, screen printing method, bar coater method, brush coating, sponge coating, etc. Conventionally known coating methods can be used. In order to improve adhesion, an intermediate layer may be coated before coating the coating composition (material adsorption and / or separation material) on the substrate.

The film thickness of the coating film (substance separation film) formed by coating is not particularly limited, and is preferably from 100 to 10 μm, more preferably from 200 to 1.5 μm, from the viewpoint of material separation characteristics.

The substrate that can be coated is not particularly limited, and the material thereof is metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, paper, combinations thereof, laminates thereof, and coatings thereof. Examples include the body.

The thus obtained material separation membrane of the present invention is a membrane made of a monoporous or porous coordination polymer having an average diameter of about 8 to 100 nm (particularly about 10 to 50 nm). Such a material separation membrane of the present invention can be applied to molecular sensing, drug delivery, etc. in addition to substance (particularly gas) adsorption, substance (particularly gas) separation, substance (particularly gas) occlusion, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to a following example. Analysis and evaluation in the examples were carried out by the following methods.

Synthesis Example 1: Synthesis of ligand compound 1 (organic ligand 1)

In the formula, TBDMS-Cl represents tert-butyldimethylsilyl chloride. DMF represents dimethylformamide.

Commercially available 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid (CDPA; 0.50 g, 1.2 mmol), tert-butyldimethylsilyl chloride (TBDMS-Cl; 0.20 g, 1.4 mmol), and imidazole ( 0.17 g, 2.5 mmol) was dissolved in dimethylformamide (DMF; 3 mL) and reacted at room temperature for 12 hours. Thereafter, water (5 mL) was added to stop the reaction, and the organic phase was extracted with ethyl acetate (5 mL × 3 times). Further, the extracted organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dehydrated by adding anhydrous magnesium sulfate. The solution was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using chloroform as a mobile phase to obtain a CDPA-protected TBDMS (CDPA-TBDMS) (0.58 g, 92%).
¹ H NMR (400 MHz, CDCl ₃ , using JEOL ECX-400, solvent peak as internal standard): ^TM (ppm) 3.33 (tr, 2H), 2.63 (tr, 2H), 2.52-2.40 (m, 1H), 2.39-2.28 (m, 1H), 1.88 (s, 3H), 1.73-1.64 (m, 2H), 1.45-1.22 (m, 21H), 0.94 (s, 9H), 0.88 (tr, 3H) , 0.27 (s, 6H).

In the formula, DMF represents dimethylformamide. THF represents tetrahydrofuran.

The obtained CDPA-TBDMS (0.2 g, 0.39 mmol) was dissolved in dichloromethane (1 mL), the solution was cooled to 0 ° C. with an ice-water bath, and 1 or 2 drops of DMF were added (catalyst). To this, a solution of oxalyl chloride ((COCl) ₂ ; 40.6 μL, 0.47 mmol) dissolved in 0.1 mL of dichloromethane was added dropwise little by little (at this time, carbon monoxide gas was generated as a by-product) ). The solution was allowed to react for 3 hours while gradually returning to room temperature, and then the solvent was completely distilled off.

Next, a solution in which 5-hydroxyisophthalic acid (70 mg, 0.39 mmol) and pyridine (78 μL) were dissolved in tetrahydrofuran (THF; 1 mL) was added thereto. The solution was reacted in a nitrogen atmosphere for 12 hours while being heated in an oil bath maintained at 45 ° C. Thereafter, water (3 mL) was added to the reaction solution to stop the reaction, chloroform (3 mL) was added to extract the product (3 mL × 3 times), and the organic phase was dehydrated with anhydrous magnesium sulfate. The solution was filtered, and the solvent was distilled off under reduced pressure. Then, the residue was purified by silica gel column chromatography using chloroform as a mobile phase to obtain Target 1 (50 mg, 23%).
¹ H NMR (400 MHz, CDCl ₃ , using JEOL ECX-400, solvent peak as internal standard): ^TM (ppm) 8.67 (s, 1H), 8.03 (s, 2H), 3.39 (tr, 2H) , 2.97 (tr, 2H), 2.79-2.64 (m, 1H), 2.58-2.48 (m, 1H), 1.97 (s, 3H), 1.80-1.68 (m, 2H), 1.48-1.20 (m, 21H) , 0.89 (tr, 3H).

Synthesis Example 2: Synthesis of organometallic polyhedral MOP1

In the formula, Cu (OAc) ₂ .H ₂ O represents copper acetate monohydrate. DMF represents dimethylformamide.

After dissolving the organic ligand 1 (24 mg) and copper acetate monohydrate (8.4 mg) obtained in Synthesis Example 1 in DMF (1 ml), they were mixed and stirred at room temperature for 3 hours. . Thereafter, methanol (4 mL) was added to the reaction solution to precipitate a solid. The precipitated solid was precipitated using a centrifuge, the supernatant was discarded, and then dissolved again in THF (1 mL). To the obtained THF solution, 4 mL of methanol was added again to precipitate a solid. This operation was repeated three times to confirm that MOP1 (19 mg) was finally obtained as a blue powder. The obtained MOP1 was vacuum dried at 50 ° C.

Example 1: Synthesis of polymer chain-introduced organometallic polyhedra

In the formula, AIBN represents azobisisobutyronitrile.

MOP1 (5 mg) obtained in Synthesis Example 2 and methyl methacrylate monomer (0.16 kg) were dissolved in toluene (1 ml). MOP1 is insoluble in toluene, but can be dissolved in a small amount when mixed with methyl methacrylate. To this was added a 0.1 M toluene solution (80 μL) of azobisisobutyronitrile (AIBN). The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was polymerized for 4 hours with stirring. Thereafter, the solution was quenched with liquid nitrogen to stop the reaction, and the solution was poured into methanol (20 mL) to precipitate a polymer. The precipitate was collected by filtration, dissolved in THF, and then poured into methanol again to precipitate the polymer (reprecipitation purification). The precipitated solid was collected by filtration and vacuum dried at 50 ° C. to confirm that a polymer graft MOP (MOP1-graft-PMMA) was obtained (33 mg).

Example 2
A part of the reaction solution of Example 1 was taken out after 65 minutes from the start of the reaction to obtain a polymer graft MOP.

Example 3
A part of the reaction solution of Example 1 was taken out after 130 minutes from the start of the reaction to obtain a polymer graft MOP.

Example 4
A part of the reaction solution of Example 1 was taken out after 205 minutes from the start of the reaction to obtain a polymer graft MOP.

Example 5
A part of the reaction solution of Example 1 was taken out after 265 minutes from the start of the reaction to obtain a polymer graft MOP.

Synthesis Example 3: Decomposition of MOP1 In the THF solution (1 mg / 1 mL) of the polymer graft MOP obtained in Example 1, N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) in THF Add about 10 μL of solution (10 μL / 1 mL) and let stand for about 10 minutes to decompose only the MOP1 part, confirming that an organic ligand with a structure in which methyl methacrylate is polymerized to organic ligand 1 was obtained did.

Synthesis Examples 4 to 7: Decomposition of polymer chain-introduced organometallic polyhedron Synthesis Example 3 except that the polymer graft MOP obtained in Examples 2 to 5 was used in place of the polymer graft MOP obtained in Example 1 It was confirmed that an organic ligand having a structure in which methyl methacrylate was polymerized on the ligand compound 1 was obtained.

Example 6: Production of a material separation membrane (production of a self-supporting film)
The polymer graft MOP obtained in Example 5 was dissolved in chloroform to a concentration of 10 mg / mL, and the resulting solution was drop-cast on a glass substrate as a coating composition and dried at room temperature. The material separation membrane was obtained by peeling the glass substrate. The appearance is shown in FIG.

Example 7: Production of a material separation membrane (production of a film for TEM observation)
The polymer graft MOP obtained in Example 5 was dissolved in chloroform so that the concentration was 5 mg / mL, and the obtained solution was drop-cast on a copper grid as a coating composition, and dried at room temperature. A material separation membrane was obtained.

Example 8: Production of a material separation membrane (production of a film for AFM observation)
The polymer graft MOP obtained in Example 5 was dissolved in chloroform so as to have a concentration of 5 mg / mL, and the obtained solution was dropped on a glass substrate as a coating composition, and dried at room temperature. A material separation membrane was obtained.

Example 9 Synthesis of Polymer Chain-Introduced Organometallic Polyhedron MOP1 (5 mg) and n-butyl methacrylate monomer (0.23 g) obtained in Synthesis Example 2 were dissolved in toluene (1 mL). A 0.1 M toluene solution (80 μL) of azobisisobutyronitrile (AIBN) was added thereto. The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was polymerized for 2 hours with stirring. Thereafter, the solution was quenched with liquid nitrogen to stop the reaction, and the solution was poured into methanol (20 mL) to precipitate a polymer. The precipitate was collected by filtration, dissolved in THF, and then poured into methanol again to precipitate the polymer (reprecipitation purification). The precipitated solid was collected by filtration and vacuum dried at 50 ° C. to confirm that a polymer graft MOP (MOP1-graft-PBMA) was obtained (41 mg).

Example 10: Synthesis of copolymer polymer chain-introduced organometallic polyhedron MOP1-graft-PBMA (10 mg) and styrene monomer (0.2 g) obtained in Example 9 were dissolved in toluene (1 mL). A 0.1 M toluene solution (80 μL) of azobisisobutyronitrile (AIBN) was added thereto. The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was allowed to polymerize for 2 hours 30 minutes with stirring. Thereafter, the solution was quenched with liquid nitrogen to stop the reaction, and the solution was poured into methanol (20 mL) to precipitate a polymer. The precipitate was collected by filtration, dissolved in THF, and then poured into methanol again to precipitate the polymer (reprecipitation purification). The precipitated solid was collected by filtration and vacuum dried at 50 ° C. to confirm that a polymer graft MOP (MOP1-graft- (PBMA-b-PSt)) was obtained (17 mg).

Synthesis Example 8 Decomposition of Polymer Chain-Introduced Organometallic Polyhedron N, N, N ', N ", N" -pentamethyldiethylenetriamine was added to the THF solution (1 mg / 1 mL) of the polymer graft MOP obtained in Example 9. Add about 10 μL of (PMDETA) THF solution (10 μL / 1 mL) and leave it for about 10 minutes to decompose only the MOP1 part, and to form an organic ligand with a structure in which butyl methacrylate is polymerized to ligand compound 1. Obtained.

Synthesis Example 9: Decomposition of Copolymer Polymer Chain-Introduced Organometallic Polyhedron To the THF solution (1 mg / 1 mL) of the polymer graft MOP obtained in Example 10, N, N, N ', N ", N" -penta Add about 10 μL of a methyldiethylenetriamine (PMDETA) THF solution (10 μL / 1 mL) and let stand for about 10 minutes to decompose only the MOP1 part, and the structure is obtained by block copolymerizing butyl methacrylate and styrene to the organic ligand 1. An organic ligand was obtained.

Test example 1: Gel permeation chromatography (GPC) measurement (1)
As a measuring instrument,
Measuring equipment: HPLC Prominence manufactured by Shimadzu Corporation (Liquid feeding pump: LC-20AD, Autosampler: SIL-20A, Column oven: CTO-20AC
Detector: RI (differential refraction) detector (RID-10A)
Column used: Shodex KF-804L 2 Column temperature: 40 ° C
Mobile phase and flow rate: Tetrahydrofuran 1mL / min
It was used.

GPC measurement of the compounds obtained in Synthesis Examples 1 to 3 was performed, and the molecular weight (number average molecular weight) of each compound was measured. The result is shown in figure 2. As a result, the number average molecular weight of the ligand compound 1 (organic ligand 1) obtained in Synthesis Example 1 was 530, but the number average molecular weight was 9500 by coordinating with copper ions to form MOP1. And increased. On the other hand, when PMDETA was allowed to act on this MOP1, the number average molecular weight was again about 530. From this, it can be understood that when PMDETA is applied to an organometallic polyhedron, the organic ligands are separated one by one.

Next, GOP measurement of the organic ligand obtained by decomposing the MOP1 obtained in Synthesis Example 2, the polymer graft MOP obtained in Examples 2 to 5 and the polymer graft MOP obtained in Synthesis Examples 4 to 8 was performed. The molecular weight (number average molecular weight) of the compound was measured. The results are shown in FIGS. As a result, all of the polymer graft MOPs obtained in Examples 2 to 5 were compared with MOP1 (number average molecular weight 9500) obtained in Synthesis Example 2, and the polymer chain was introduced. (Number average molecular weight 32000), Example 3 (number average molecular weight 78200), Example 4 (number average molecular weight 121500), Example 5 (number average molecular weight 147500), it can be understood that all have increased molecular weight. . In addition, as described above, when PMDETA is allowed to act on an organometallic polyhedron, the organic ligands can be decomposed one by one. However, the compounds obtained in Synthesis Examples 4 to 8 are the organic ligands of the polymer graft MOP. Since it was decomposed one by one and the polymer chain was introduced into the original ligand compound 1 (organic ligand 1), compared with ligand compound 1 (organic ligand 1), The molecular weights of Synthesis Example 4 (number average molecular weight 3600), Synthesis Example 5 (number average molecular weight 9400), Synthesis Example 6 (number average molecular weight 13000), Synthesis Example 7 (number average molecular weight 14900) were large. In addition, since the peak width is narrow, it can be understood that the same degree of polymer chain is introduced into the organic ligand constituting the polymer graft MOP.

Test Example 2: Electron Microscope Observation The surface structure of the material separation membrane obtained in Examples 7 and 8 was observed with an electron microscope (Example 7: Transmission electron microscope (TEM), Example 8: Atomic force microscope (AFM) )). The results are shown in FIG. As a result, it can be understood that the surface is composed of particles (polymer graft MOP) of about 10 to 20 nm.

Test Example 3: Gas Adsorption / Desorption Test With respect to MOP1 obtained in Synthesis Example 2, the nitrogen adsorption amount and nitrogen desorption amount at a temperature of 77 K, and the carbon dioxide adsorption amount and the carbon dioxide desorption amount at a temperature of 195 K were measured. A Belsorp Max volumetric adsorption device manufactured by Nippon Bell Co., Ltd. was used for the measurement. The measurement was performed at a temperature of 77 K using a Belsorp Max cryosystem. The obtained result is shown in FIG. In FIG. 6, ads is an adsorption amount and des is a desorption amount. As a result, it can be understood that MOP1 selectively adsorbs and desorbs carbon dioxide as compared with nitrogen. Since the characteristic of selectively adsorbing and desorbing carbon dioxide is derived from the unique structure of MOP, the compound of the present invention into which a polymer chain is introduced also selectively absorbs and desorbs carbon dioxide. Can do.

Test example 4: Gel permeation chromatography (GPC) measurement (2)
As a measuring instrument,
Measuring equipment: HPLC Prominence manufactured by Shimadzu Corporation (Liquid feeding pump: LC-20AD, Autosampler: SIL-20A, Column oven: CTO-20AC
Detector: RI (differential refraction) detector (RID-10A)
Column used: Shodex KF-804L 2 Column temperature: 40 ° C
Mobile phase and flow rate: Tetrahydrofuran 1mL / min
It was used.

GPC measurement of the compounds obtained in Examples 9 to 10 and Synthesis Examples 8 to 9 was performed, and the molecular weight (number average molecular weight) of each compound was measured. The results are shown in FIG. In the same manner as in Example 1, in Example 9, n-butyl methacrylate monomer and MOP1 were reacted and GPC measurement was performed. As a result, it can be understood that the molecular weight is increased (number average molecular weight 132300) by introducing a polymer chain into MOP1. In Example 10, the compound (MOP1-graft-PBMA) obtained in Example 9 and the styrene monomer were reacted successively to perform GPC measurement. As a result, it can be understood that the styrene monomer is continuously introduced into MOP1-graft-PBMA, thereby further increasing the molecular weight (number average molecular weight 269300). That is, through Examples 9 and 10, it was found that a block copolymer of butyl methacrylate and styrene could be introduced into MOP1 by performing two-step RAFT polymerization from MOP1. In addition, as described above, when PMDETA is allowed to act on the organometallic polyhedron, each organic ligand can be decomposed one by one. As a result, the compound obtained in Synthesis Example 9 (number average molecular weight 14500) is the compound obtained in Synthesis Example 8 ( The molecular weight is certainly larger than the number average molecular weight 13400), which means that the living block copolymerization is proceeding on MOP1.

Test Example 5: MOP1 obtained in Diameter Synthesis Example 2, the polymer chain-introduced organometallic polyhedron obtained in Example 1, and the copolymer polymer chain-introduced organometallic polyhedron obtained in Example 8 were analyzed by Zetasizer Nano ZSP manufactured by Malvern. The diameter was measured. The results are shown in FIG. As a result, in the THF solution, MOP1 is distributed in the range of about 3 to 7 nm, the polymer chain-introduced organometallic polyhedra are in the range of about 10 to 30 nm, and the copolymer polymer chain-introduced organometallic polyhedra are in the range of about 12 to 50 nm. The average diameter was about 5 nm for MOP1, about 18 nm for the polymer chain-introduced organometallic polyhedron, and about 20 nm for the copolymer polymer chain-introduced organometallic polyhedron.

Synthesis Example 10: Synthesis of Compound 8

[Wherein t-Bu represents a tert-butyl group. ]
Compound 8 was obtained by a method according to the literature (Davis, B. G .; Shang, X .; DeSantis, G .; Bott, R. R .; Jones, J. B. Bioorg. Med. Chem. 1999, 7, 2293-2301). Yield 70%.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.48 (t, J = 1.4 Hz, isophH, 1H), 8.13 (d, J = 1.4 Hz, isophH, 2H), 4.52 (s, benzyl, 2H ), 1.59 (s, -C (CH ₃ ) ₃ , 18H). ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ (ppm) 164.6, 138.4, 133.7, 133.3, 130.4, 82.0, 32.0, 28.2.

Synthesis Example 11 Synthesis of Compound 9

Compound 9 was obtained by a method according to the literature (Kato, S .; Yamada, S .; Goto, H .; Terashima, K .; Mizuta, M .; Katada, TZ Naturforsch. B 1980, 35, 458-462) . Yield 98%.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.43-8.35 (m, 2H), 7.26-7.18 (m, 1H), 7.16-7.08 (m, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 253.5, 153.7, 128.9, 127.7, 126.8.

Synthesis Example 12: Synthesis of ligand compound 2 (organic ligand 2)

In the formula, t-Bu represents a tert-butyl group.

Compound 9 (3.6 g, 18.7 mmol) obtained in Synthesis Example 11 is added to an acetone solution (50 mL) of Compound 8 (5.3 g, 14.4 mmol) obtained in Synthesis Example 10, and the mixture is stirred at room temperature for 3 hours under a nitrogen atmosphere. did. After adding 20 mL of water to the reaction solution and concentrating to about 15 mL with a rotary evaporator, the residue was extracted with ethyl acetate. The extracted organic phase was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure with a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain the target compound 10. Yield 94%.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.48 (t, J = 1.4 Hz, isophH, 1H), 8.16 (d, J = 1.4 Hz, isophH, 2H), 8.01-7.99 (m, ArH , 2H), 7.56-7.52 (m, ArH, 1H), 7.41-7.37 (m, ArH, 2H), 4.66 (s, benzyl, 2H), 1.60 (s, -C (CH 3) 3, 18H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 226.8, 164.7, 144.5, 135.8, 133.9, 132.7, 132.6, 129.8, 128.4, 126.9, 81.8, 41.2, 28.1. ESI-MS (methanol with a trace amount of KI, positive mode): calcd. for [M + K] ⁺ , m / z = 483.11; found m / z = 483.13.

In the formula, t-Bu represents a tert-butyl group. TFA indicates trifluoroacetic acid.

To a dichloromethane solution (15 mL) of compound 10 (6.67 g, 15 mmol) was added a dichloromethane solution (15 mL) of trifluoroacetic acid (TFA; 18.4 mL, 240 mmol), and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. The formed precipitate was collected by filtration and washed with dichloromethane and water on a funnel. The obtained powdery solid was dried at 80 ° C. under reduced pressure for 24 hours to obtain Ligand Compound 2 (Organic Ligand 2). Yield 96%.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 8.38 (t, J = 1.8 Hz, isophH, 1H), 8.23 (d, J = 1.8 Hz, isophH, 2H), 7.99-7.94 (m , ArH, 2H), 7.67-7.60 (m, ArH, 1H), 7.51-7.42 (m, ArH, 2H), 4.84 (s, benzyl, 2H). ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ (ppm) 227.0, 166.3, 143.9, 137.0, 134.0, 133.2, 131.5, 129.1, 128.8, 126.6, (the benzyl carbon signal was overlapped with a solvent signal.). ESI-MS (methanol, negative mode): calcd. for [M-H] ^- , m / z = 331.01; found m / z = 331.03.

Synthesis Example 13: Synthesis of ligand compound 3 (organic ligand 3)

In the formula, t-Bu represents a tert-butyl group.

Potassium phosphate (1.63 g, 7.7 mmol) was suspended in acetone (10 mL) and stirred. 1-butanethiol (CH ₃ (CH ₂ ) ₂ CH ₂ SH; 0.83 mL, 7.7 mmol) was added thereto, and then carbon disulfide (CS ₂ ; 0.47 mg, 7.7 mmol) was added dropwise with stirring, followed by nitrogen. Stir for 3 hours at room temperature under atmosphere. To this solution was added an acetone solution (8 mL) of compound 8 (2.60 g, 7.0 mmol) obtained in Synthesis Example 10, and the mixture was further stirred at room temperature for 16 hours. Water (20 mL) was added, the solution was concentrated on a rotary evaporator, and the residue was extracted with ethyl acetate. The organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography to obtain the target compound 11. Yield 88%.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.46 (t, J = 1.8 Hz, isophH, 1H), 8.11 (d, J = 1.8 Hz, isophH, 2H), 4.67 (s, benzyl, 2H ), 3.39 (t, J = 7.3 Hz, S = CS-CH _2- , 2H), 1.69 (quin., J = 7.3 Hz, S = CS-CH ₂ -CH _2- , 2H), 1.60 (s, -C (CH ₃ ) ₃ , 18H), 1.43 (sext., J = 7.3 Hz, -CH ₂ -CH ₂ -CH ₃ , 2H), 0.94 (t, J = 7.3 Hz, -CH ₂ -CH ₃ , ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 223.1, 164.8, 136.2, 134.0, 132.8, 129.9, 81.9, 40.4, 37.1, 30.1, 28.1, 22.2, 13.7. ESI-MS (methanol with a trace amount of KI, positive mode): calcd. for [M + K] ⁺ , m / z = 495.11; found m / z = 495.15.

A dichloromethane solution (15 mL) of trifluoroacetic acid (TFA; 1.4 mL, 18.3 mmol) was added to a dichloromethane solution (15 mL) of compound 11 (3.54 g, 7.75 mmol), and the mixture was stirred at room temperature for 1.5 hours under a nitrogen atmosphere. The formed precipitate was collected by filtration and washed with hexane and water on the funnel. The obtained powdered solid was dried under reduced pressure at 30 ° C. for 24 hours to obtain a ligand compound 3 (organic ligand 3). Yield 94%.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 13.6-13.0 (br, -COOH, 2H), 8.56 (d, J = 1.4 Hz, isophH, 1H), 8.17 (d, J = 1.4 Hz, isophH, 2H), 4.82 (s, benzyl, 2H), 3.38 (t, J = 7.3 Hz, S = CS-CH _2- , 2H), 1.61 (quin., J = 7.3 Hz, S = CS- CH ₂ -CH _2- , 2H), 1.34 (sext., J = 7.3 Hz, -CH ₂ -CH ₂ -CH ₃ , 2H), 0.86 (t, J = 7.3 Hz, -CH ₂ -CH ₃ , 3H ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ (ppm) 223.3, 166.3, 137.4, 134.0, 131.5, 129.1, 39.0, 36.3, 29.6, 21.4, 13.4. ESI-MS (methanol, negative mode) : calcd. for [M-H] ^- , m / z = 343.01; found m / z = 343.03.

Synthesis Example 14: Synthesis of ligand compound 4 (organic ligand 4)

In the formula, t-Bu represents a tert-butyl group.

First, using potassium propanedithioate and ethylmagnesium bromide as raw materials, the literature (Kato, S .; Yamada, S .; Goto, H .; Terashima, K .; Mizuta, M .; Katada, TZ Naturforsch. B 1980 , 35, 458-462).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 3.01 (q, J = 7.3 Hz, -CH ₂ CH ₃ , 2H), 1.25 (t, J = 7.3 Hz, -CH ₂ CH ₃ , 3H).

Next, potassium propanedithioate (76 mg, 0.53 mmol) was added to an acetone solution (1.5 mL) of compound 8 (150 mg, 0.40 mmol) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 1 hour. After the reaction solution was concentrated to dryness on a rotary evaporator, the product was purified by silica gel column chromatography and dried at 40 ° C. under reduced pressure for 16 hours to obtain the target compound 12 (yield 154 mg, tan solid, Yield 96%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.46 (t, J = 1.4 Hz, isophH, 1H), 8.09 (d, J = 1.4 Hz, isophH, 2H), 4.52 (s, benzyl, 2H ), 3.03 (q, J = 7.3 Hz, -CH ₂ CH ₃ , 2H), 1.60 (s, -C (CH ₃ ) ₃ , 18H), 1.38 (t, J = 7.3 Hz, -CH ₂ CH ₃ , 3H).

A dichloromethane solution (0.8 mL) of trifluoroacetic acid (TFA; 0.39 mL, 5.0 mmol) was added to a dichloromethane solution (0.8 mL) of compound 12 (154 mg, 0.39 mmol), and the mixture was stirred at room temperature for 1 hour. The formed precipitate was collected by filtration, and washed on the funnel with a mixture of ethyl acetate / hexane (1/50, v / v). The obtained powdery solid was dried under reduced pressure at 40 ° C. for 16 hours to obtain ligand compound 4 (organic ligand 4) (yield 87 mg, light yellow solid, yield 79%).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 13.4-13.2 (br, -COOH, 2H), 8.36 (t, J = 1.8 Hz, isophH, 1H), 8.15 (d, J = 1.8 Hz, isophH, 2H), 4.69 (s, benzyl, 2H), 3.03 (q, J = 7.3 Hz, -CH ₂ CH ₃ , 2H), 1.28 (t, J = 7.3 Hz, -CH ₂ CH ₃ , 3H ).

Synthesis Example 15: Synthesis of ligand compound 5 (organic ligand 5)

In the formula, t-Bu represents a tert-butyl group.

Sodium dithiocarbamate trihydrate (3.13 g, 13.9 mmol) was added to an acetone solution (80 mL) of compound 8 (4.0 g, 10.7 mmol) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 16 hours. After adding 80 mL of water to the reaction solution and distilling off acetone with a rotary evaporator, the residue was extracted with dichloromethane (40 mL × 2 times). The extracted organic phase was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure using a rotary evaporator, followed by drying at 40 ° C. under reduced pressure for 16 hours to obtain the target compound 13 (yield 4.69 g, white solid, 99% yield). .
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.46 (t, J = 1.6 Hz, isophH, 1H), 8.16 (d, J = 1.6 Hz, isophH, 2H), 4.61 (s, benzyl, 2H ), 4.04 (q, J = 7.3 Hz, -N (CH ₂ CH ₃ ) ₂ , 2H), 3.73 (q, J = 7.3 Hz, -N (CH ₂ CH ₃ ) ₂ , 2H), 1.60 (s, _{_{-C (CH 3) 3, 18H}} ), 1.29 (t, J = 7.3 Hz, -N (CH 2 CH 3) 2, 6H).

A dichloromethane solution (11 mL) of trifluoroacetic acid (TFA; 11 mL, 144 mmol) was added to a dichloromethane solution (22 mL) of compound 13 (4.69 g, 10.7 mmol), and the mixture was stirred at room temperature for 1 hour. The formed precipitate was collected by filtration and washed on the funnel with water and dichloromethane. The obtained powdery solid was dried at 80 ° C. under reduced pressure for 16 hours to obtain a ligand compound 5 (organic ligand 5) (yield 3.16 g, white solid, yield 91%).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 13.4-13.2 (br, -COOH, 2H), 8.35 (t, J = 1.8 Hz, isophH, 1H), 8.18 (d, J = 1.8 Hz, isophH, 2H), 4.71 (s, benzyl, 2H), 3.97 (q, J = 7.3 Hz, -N (CH ₂ CH ₃ ) ₂ , 2H), 3.75 (q, J = 7.3 Hz, -N ( CH ₂ CH ₃ ) ₂ , 2H), 1.21 (t, J = 7.3 Hz, -N (CH ₂ CH ₃ ) ₂ , 3H), 1.16 (t, J = 7.3 Hz, -N (CH ₂ CH ₃ ) ₂ , 3H).

Synthesis Example 16: Synthesis of ligand compound 6 (organic ligand 6)

In the formula, t-Bu represents a tert-butyl group.

Potassium xanthate (1.68 g, 10.5 mmol) was added to an acetone solution (30 mL) of compound 8 (3.0 g, 8.1 mmol) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated and dried with a rotary evaporator, and then dissolved again in ethyl acetate (50 mL), and the organic phase was washed with water (30 mL × 2 times). The organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure using a rotary evaporator, and the product was purified by silica gel column chromatography. The product was dried under reduced pressure at 40 ° C. for 16 hours to obtain the target compound 14 (yield 3.24 g, light yellow solid, yield 97%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.47 (t, J = 1.8 Hz, isophH, 1H), 8.12 (d, J = 1.8 Hz, isophH, 2H), 4.65 (q, J = 7.3 Hz, -OCH ₂ CH ₃ , 2H), 4.40 (s, benzyl, 2H), 1.60 (s, -C (CH ₃ ) ₃ , 18H), 1.44 (t, J = 7.3 Hz, -OCH ₂ CH ₃ , 3H).

A dichloromethane solution (0.77 mL) of trifluoroacetic acid (TFA; 0.38 mL, 4.98 mmol) was added to a dichloromethane solution (0.77 mL) of compound 14 (158 mg, 0.38 mmol), and the mixture was stirred at room temperature for 1 hour. The formed precipitate was collected by filtration, washed with hexane on the funnel, and then washed with a mixed solution of ethyl acetate / hexane (1/30, v / v). The obtained powdery solid was dried under reduced pressure at 40 ° C. for 16 hours to obtain ligand compound 6 (organic ligand 6) (yield 98 mg, white solid, yield 85%).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 13.4-13.2 (br, -COOH, 2H), 8.36 (t, J = 1.8 Hz, isophH, 1H), 8.19 (d, J = 1.8 Hz, isophH, 2H), 4.60 (q, J = 7.3 Hz, -OCH ₂ CH ₃ , 2H), 4.53 (s, benzyl, 2H), 1.36 (t, J = 7.3 Hz, -OCH ₂ CH ₃ , 3H ).

Synthesis Example 17: Synthesis of ligand compound 7 (organic ligand 7)

In the formula, t-Bu represents a tert-butyl group.

First, using potassium 2,5-dimethylbenzenecarbodithioate and 2,5-dimethylphenylmagnesium bromide as raw materials, the literature (Kato, S .; Yamada, S .; Goto, H .; Terashima, K .; Mizuta , M .; Katada, TZ Naturforsch. B 1980, 35, 458-462).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 6.82-6.79 (m, ArH, 1H), 6.72-6.68 (s, ArH, 2H), 2.18 (s, Ar-CH ₃ , 6H) .

Next, potassium 2,5-dimethylbenzenecarbodithioate (2.0 g, 9.1 mmol) was added to an acetone solution (40 mL) of compound 8 (2.25 g, 6.1 mmol) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 20 hours. Stir. The reaction solution was concentrated and dried with a rotary evaporator, and then dissolved again in ethyl acetate (50 mL), and the organic phase was washed with water (30 mL × 2 times). The organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure using a rotary evaporator, and the product was purified by silica gel column chromatography. The resulting black-brown product was suspended in cold hexane, washed, filtered, and dried under reduced pressure at 40 ° C. for 16 hours to obtain the target compound 15 (yield 1.16 g, bright yellow solid, 40% yield). ).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.48 (t, J = 1.4 Hz, isophH, 1H), 8.14 (d, J = 1.4 Hz, isophH, 2H), 7.10-7.08 (m, ArH , 2H), 7.07-7.05 (m, ArH, 1H), 4.64 (s, benzyl, 2H), 2.31 (s, Ar-CH 3, 6H), 1.61 (s, -C (CH 3) 3, 18H) .

A dichloromethane solution (10 mL) of trifluoroacetic acid (TFA; 0.95 mL, 12.4 mmol) was added to a dichloromethane solution (13 mL) of compound 15 (2.34 g, 4.95 mmol), and the mixture was stirred at room temperature for 3 hours. The formed precipitate was collected by filtration, and washed on the funnel with water and a mixed solution of ethyl acetate / hexane (1/30, v / v). The obtained powdery solid was dried at 40 ° C. under reduced pressure for 16 hours to obtain a ligand compound 7 (organic ligand 7) (yield 1.7 g, bright yellow solid, yield 96%).
¹ H NMR (400 MHz, DMSO-d ₆ ): δ (ppm) 13.0-13.6 (br, -COOH, 2H), 8.38 (t, J = 1.8 Hz, isophH, 1H), 8.22 (d, J = 1.8 Hz, isophH, 2H), 7.16-7.12 (m, ArH, 2H), 7.03-6.98 (m, ArH, 1H), 4.81 (s, benzyl, 2H), 2.27 (s, Ar-CH ₃ , 3H), 2.20 (s, -CH ₃ , 3H).

Synthesis Example 18: Synthesis of organometallic polyhedral MOP2

In the formula, Cu (OAc) ₂ .H ₂ O represents copper acetate monohydrate. NMP represents N-methylpyrrolidone.

An organometallic polyhedral MOP2 was obtained in the same manner as in Synthesis Example 2, except that the ligand compound 3 (organic ligand 3) obtained in Synthesis Example 13 was used as a raw material and N-methylpyrrolidone was used as a solvent. It was.

Example 11: Synthesis of polymer chain-introduced organometallic polyhedra

Polymer grafting was carried out in the same manner as in Example 1, except that MOP2 obtained in Synthesis Example 18 was used as the raw material, tert-butyl acrylate was used as the monomer compound, tetrahydrofuran was used as the solvent, and the reaction time was 15 minutes. MOP (MOP2-graft-PtBA39) was obtained. In addition, since this polymer graft MOP is also highly soluble in a solvent, a film can be produced by coating and drying.

Example 12
A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 45 minutes.

Example 13
A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 75 minutes.

Example 14
A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was changed to 105 minutes.

Example 15
A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 135 minutes.

Synthesis Examples 19 to 23: Decomposition of polymer chain-introduced organometallic polyhedra Synthesis Example 3 except that the polymer graft MOP obtained in Examples 11 to 15 was used instead of the polymer graft MOP obtained in Example 1 It was confirmed that an organic ligand having a structure in which tert-butyl acrylate was polymerized to the ligand compound 2 was obtained.

Test Example 6: Gel permeation chromatography (GPC) measurement (Part 3)
As a measuring instrument,
Measuring equipment: HPLC Prominence manufactured by Shimadzu Corporation (Liquid feeding pump: LC-20AD, Autosampler: SIL-20A, Column oven: CTO-20AC
Detector: RI (differential refraction) detector (RID-10A)
Column used: Shodex KF-804L 2 Column temperature: 40 ° C
Mobile phase and flow rate: Tetrahydrofuran 1mL / min
It was used.

GPC measurement of the compounds obtained in Examples 11 to 15 and Synthesis Examples 18 to 23 was performed, and the molecular weight (number average molecular weight) of each compound was measured. The results are shown in FIG. In the same manner as in Example 1, in Examples 11 to 15, tert-butyl acrylate monomer and MOP2 were reacted and GPC measurement was performed. As a result, in comparison with MOP2 obtained in Synthesis Example 18 (number average molecular weight 5090 g / mol), Example 11 (number average molecular weight 6500 g / mol) was carried out by introducing a polymer chain. Example 12 (number average molecular weight 18000 g / mol), Example 13 (number average molecular weight 30700 g / mol), Example 14 (number average molecular weight 46800 g / mol), Example 15 (number average molecular weight 59200 g / mol) It can be understood that both increase in molecular weight. In addition, as described above, when PMDETA is allowed to act on the organometallic polyhedron, the organic ligands can be decomposed one by one. The compounds obtained in Synthesis Examples 19 to 23 are the organic ligands of the polymer graft MOP. Since it was decomposed one by one and a polymer chain was introduced into the original ligand compound 3 (organic ligand 3), compared with ligand compound 3 (organic ligand 3), Synthesis example 19 (number average molecular weight 880 g / mol), synthesis example 20 (number average molecular weight 2030 g / mol), synthesis example 21 (number average molecular weight 3080 g / mol), synthesis example 22 (number average molecular weight 4500 g / mol) ), Synthesis Example 23 (number average molecular weight 5800 g / mol) and molecular weight were large. In addition, since the peak width is narrow, it can be understood that the same degree of polymer chain is introduced into the organic ligand constituting the polymer graft MOP.

From these results, a plot of the polymerization reaction time and the monomer conversion rate is shown in FIG. 10 (a), and a plot of the monomer conversion rate and the MOP number average molecular weight is shown in FIG. 10 (b) (●: number average molecular weight, ■: molecular weight. In the dispersion (Mw / Mn)), the monomer conversion rate and the number average molecular weight of the decomposed organic ligand are plotted in FIG. 10 (c) (●: number average molecular weight, ■: molecular weight dispersion (Mw / Mn)). Each is shown. As can be seen from FIG. 10 (b), as the monomer conversion increases (polymerization proceeds), the molecular weight increases linearly and the molecular weight dispersion is always close to 1, so the reaction is a living mechanism. It is suggested that it is progressing.

Example 16
Ligand compound 2 (organic ligand 2) obtained in Synthesis Example 12 instead of ligand compounds 1 and 3 (organic ligands 1 and 3) as the ligand compound (organic ligand) A polymer graft MOP was obtained in the same manner as in Example 1 except that was used. It was also confirmed that polymer graft MOP was obtained by this method. In addition, since this polymer graft MOP is also highly soluble in a solvent, a film can be produced by coating and drying.

In addition, as a ligand compound (organic ligand), instead of ligand compounds 1 and 3 (organic ligands 1 and 3), ligand compound 4 (organic ligand) obtained in Synthesis Example 14 4), ligand compound 5 obtained in Synthesis Example 15 (organic ligand 4), ligand compound 6 obtained in Synthesis Example 16 (organic ligand 6), ligand obtained in Synthesis Example 17 Similar results are expected to be obtained when compound 7 (organic ligand 7) or the like is used.

Claims

General formula (1):

[Wherein, m represents an integer of 1 to 3. X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group. X 2 represents a single bond or a divalent linking group. R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different. R 2 is

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. ]
A ligand compound represented by:
R 2 is

The ligand compound of Claim 1 which is group represented by these.
X 2 represents the general formula (2):

[Wherein R 3 represents a hydrogen atom or an optionally substituted alkyl group. R 4 represents a hydrogen atom, an optionally substituted alkyl group or a cyano group. X 3 represents a single bond, an optionally substituted alkylene group, or a group represented by —R 5 —COO— (R 5 represents an optionally substituted alkylene group). ]
The ligand compound of Claim 1 or 2 which is group represented by these.
Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring. Yes,
Said monocyclic or condensed and COO - in the binding of the group, the general formula (6):

[Wherein R 8 is the same or different and represents a carbon atom or a nitrogen atom. R 9 represents a divalent aromatic hydrocarbon group which may be substituted. k represents an integer of 0-2. ]
The ligand compound according to any one of claims 1 to 3, which may contain a group represented by:
Bivalent or higher metal ions and general formula (3):

[Wherein, m represents an integer of 1 to 3. X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group. X 2 represents a single bond or a divalent linking group. R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different. R 2 is

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. Z is the same or different and represents an optionally substituted ethylene chain. n represents an integer of 5 to 20000. ]
A monoporous or porous coordination polymer comprising an organic ligand represented by the formula (1) and wherein the metal ion and the organic ligand are alternately coordinated.
R 2 is

The monoporous or porous coordination polymer according to claim 5, which is a group represented by:
X 2 represents the general formula (2):

[Wherein R 3 represents a hydrogen atom or an optionally substituted alkyl group. R 4 represents a hydrogen atom, an optionally substituted alkyl group or a cyano group. X 3 represents a single bond, an optionally substituted alkylene group, or a group represented by —R 5 —COO— (R 5 represents an optionally substituted alkylene group). ]
The monoporous or porous coordination polymer according to claim 5 or 6, which is a group represented by the formula:
Said Z is the general formula (4):

[Wherein R 6 represents a hydrogen atom or an optionally substituted alkyl group. R 7 is a hydroxyl group, an optionally substituted carboxy group, an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl Indicates a group. ]
The monoporous or porous coordination polymer according to any one of claims 5 to 7, which is a chain represented by
The monoporous or porous coordination polymer according to any one of claims 5 to 8, comprising the metal ion and the organic ligand.
The monoporous or porous coordination polymer according to any one of claims 5 to 9, comprising 4 or more metal ions and 4 or more organic ligands.
The monoporous or porous coordination polymer according to any one of claims 5 to 10, wherein the metal ion is a divalent metal ion.
The monoporous or porous coordination polymer according to any one of claims 5 to 11, wherein the metal ion is a transition metal ion.
The metal ion is at least one selected from the group consisting of copper ion, zinc ion, cobalt ion, cadmium ion, rhodium ion, calcium ion, magnesium ion, manganese ion, nickel ion, palladium ion, lanthanum ion, and zirconium ion. The monoporous or porous coordination polymer according to any one of claims 5 to 12, wherein
Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring. Yes,
Said monocyclic or condensed and COO - in the binding of the group, the general formula (6):

[Wherein R 8 is the same or different and represents a carbon atom or a nitrogen atom. R 9 represents a divalent aromatic hydrocarbon group which may be substituted. k represents an integer of 0-2. ]
The monoporous or porous coordination polymer according to any one of claims 5 to 13, which may contain a group represented by:
The monoporous or porous coordination polymer according to any one of claims 5 to 14, which is an organometallic polyhedron.
The monoporous or porous coordination polymer according to claim 15, having an average diameter of 2 nm to 100 nm.
The monoporous or porous coordination polymer according to claim 15 or 16, which has one pore having an average diameter of 2 nm or less inside.
A method for producing an organometallic polyhedron having polymer chains introduced therein,
Using an organometallic polyhedron and a monomer compound, and a step of performing reversible addition-fragmentation chain transfer polymerization,
The organometallic polyhedron has a divalent or higher valent metal ion and a general formula (5):

[Wherein, m represents an integer of 1 to 3. X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group. X 2 represents a single bond or a divalent linking group. R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different. R 2 is

The group represented by these is shown. Y represents an aromatic hydrocarbon ring or a heteroaromatic ring. ]
And a metal ion and the organic ligand are alternately coordinate-bonded to each other.
A material for adsorbing and / or separating a substance comprising the monoporous or porous coordination polymer according to any one of claims 5 to 17.
The material for adsorbing and / or separating a substance according to claim 19, which is at least one selected from the group consisting of a gas and / or ion adsorbing material and a gas and / or ion separating material.
A substance separation membrane comprising the monoporous or porous coordination polymer according to any one of claims 5 to 17, or the substance adsorption and / or separation material according to claim 19 or 20.
The substance separation membrane according to claim 21, which is a gas and / or ion separation membrane.