JP2017149682A - Porous polymer metal complex, and gas absorbent, gas separation device, gas storage device, catalyst, conductive material and sensor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous polymer metal complex, and a gas absorber, a gas storage device and a gas separation device using the same and having excellent properties.SOLUTION: There is provided a porous polymer metal complex having a constitutional unit of [AXY], where A represents a transition metal ion, X represents a first ligand which is an isophthalic acid ion having a functional group containing halogen other than fluorine at the 5-position, Y represents a bipyridyl second ligand having ligand points in both terminals of the molecule and n represents the number of constitutional units consisting of AXY.SELECTED DRAWING: None

Description

  The present invention relates to use as a porous polymer metal complex and a gas adsorbing material, and a gas separation device and a gas storage device using the same.

  The gas adsorbent has a characteristic of storing a large amount of gas at a low pressure as compared with pressurized storage and liquefied storage. For this reason, in recent years, development of a gas storage device and a gas separation device using a gas adsorbent has been active. As the gas adsorbent, activated carbon, zeolite and the like are known. Recently, a method of occluding gas in a porous polymer metal complex has also been proposed (see Patent Document 1 and Non-Patent Document 1).

  Porous polymer metal complexes are crystalline solids composed of metal ions and organic ligands, and exhibit various gas adsorption properties due to the variety of metal ions and combinations of organic ligands and the variety of skeletal structures. There is a possibility to do. However, these conventionally proposed gas adsorbents are not sufficiently satisfactory in terms of the amount of gas adsorption and workability, and the development of gas adsorbents with better characteristics is desired. .

  Since an enormous amount of oxygen is used as an industrial gas in industries such as steel, development of an oxygen separation method is very important. For this purpose, so-called porous bodies having a large number of small pores are used as adsorbents, but most adsorbents that adsorb oxygen also adsorb gases other than oxygen, such as nitrogen. There are many things. In particular, when the temperature is lowered, the interaction between the pores and various gases becomes stronger, so in principle many porous bodies adsorb various gases. It is not well known whether an adsorbent that selectively adsorbs only can be produced. Oxygen separation using molecular sieve carbon and PSA (Pressure Swing Adsorption) equipment has been put to practical use, but there is a great need for miniaturization and high efficiency, and it is important to develop a high-performance oxygen separator to meet this demand It is.

  Carbon monoxide is useful as a raw material for chemical products such as fuel and acetic acid and polycarbonate. A large amount of carbon monoxide is generated from the iron and steel industry during operations such as converters, and this is obtained as a mixed gas with nitrogen. However, the physical and chemical properties of carbon monoxide and nitrogen are very similar, and the separation efficiency of carbon monoxide and nitrogen using existing porous materials such as zeolite and activated carbon is low. Development of a high-efficiency carbon monoxide selective adsorbent that is not widespread is desired.

  Porous Coordination Polymer (PCP) obtained from metal ions and ligands has nano-scale fine pores, similar to zeolite and activated carbon, and can adsorb and separate gases. It is known. It is well known that the characteristics of the ligand affect the gas adsorption separation characteristics of PCP. Examples in which an amino group increases carbon dioxide adsorption and examples in which a fluorine atom-containing functional group increases adsorption of hydrogen, carbon dioxide, and oxygen are known (Non-patent Documents 2 to 7 and Patent Documents 2 to 2). 6). However, it is hardly known how halogen atoms other than fluorine, such as chlorine, bromine and iodine, affect the gas adsorption and separation characteristics (Non-patent Document 3). Since ions also affect the gas adsorption separation characteristics of PCP (Non-patent Document 8), an excellent gas can be obtained by creating PCP with any network structure between any metal ion and any ligand. It is not well understood whether adsorption separation characteristics can be obtained.

JP 2000-109493 A International Publication No. 2014/069574 JP 2014-169248 A JP 2014-169262 A JP 2014-166969 A JP 2014-166970 A

Susumu Kitagawa, Integrated Metal Complex, Kodansha Scientific, 2001, pages 214-218 Omary et al., J. Am. Chem. Soc., 2007,129, 15454 Navarro et al., Chem. Eur. J. 2008, 14, 9890-9901 Bu et al., Scientific Report, DOI: 10.1038 / srep03312 Li et al., J. Am. Chem. Soc., 2004, 126, 1308 Ferey et al., J. AM. CHEM. SOC. 2010, 132, 1127-1136 Jeon et al., Chem. Commun., 2014, 50, 10861 Rosseinsky et al., Microporous and mesoporous Mater. 73, (2004), 15

  An object of the present invention is to provide a porous polymer metal complex and a gas adsorbent having excellent characteristics using the same. Another object of the present invention is to provide a gas storage device and a gas separation device that contain a gas adsorbent having the above-mentioned characteristics.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a first ligand of isophthalic acid type having a halogen-containing functional group other than fluorine at the 5-position, and a coordination point. A porous polymer metal complex obtained by the reaction of a bipyridyl-type second ligand having a hydrogen atom at both ends of the molecule with a transition metal ion is capable of oxygen and carbon monoxide in other gases over a wide temperature range. As a result, the present invention was completed. In the present invention, an element existing between a Group 3 element and a Group 12 element in the periodic table is called a transition metal.

  That is, the present invention provides an isophthalic acid type first ligand having a halogen-containing functional group other than fluorine at the 5-position, and a bipyridyl type second ligand having coordination points at both ends of the molecule. Is a porous polymer metal complex containing a transition metal ion, and is an invention relating to the use of this material as a gas storage material and a gas storage device and a gas separation device containing the gas adsorbent therein .

  That is, the present invention is as follows.

(1) [AXY] _n (1)
(In the formula, A represents a transition metal ion, X represents a first ligand which is an isophthalic acid ion having a halogen-containing functional group other than fluorine at the 5-position, and Y represents a coordination point at both ends of the molecule. Represents a bipyridyl-type second ligand possessed, and n represents the number of structural units comprising AXY)
A porous polymer metal complex having the following structural unit:
(2) The porous polymer metal complex according to (1), wherein the transition metal ion is any one of a cobalt ion, a nickel ion, a copper ion, and a zinc ion.
(3) The porous polymer metal complex according to (1), wherein the transition metal ion is a zinc ion.
(4) The porous polymer metal complex according to the above (1) or (2), wherein the halogen element of the halogen-containing functional group is chlorine, bromine, or iodine.
(5) The porous polymer metal complex according to any one of (1) to (3), wherein the halogen element of the halogen-containing functional group is iodine.
(6) The porous polymer metal complex according to any one of (1) to (5), wherein the halogen-containing functional group is a linear or branched alkyl group or alkoxy group containing a halogen element.
(7) The porous polymer metal complex according to any one of (1) to (6), wherein the halogen-containing functional group is a linear or branched alkyl group or alkoxy group having 1 to 10 carbon atoms.
(8) The porous polymer metal complex according to any one of (1) to (7), wherein the halogen-containing functional group contains any one of 1 to 21 halogen atoms.
(9) [AXY] _n (2)
(In the formula, A represents a transition metal ion, Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule, and X represents an isophthalate ion or other than fluorine at the 5-position. Represents a first ligand which is a plurality of types of isophthalic acid ions including at least one isophthalic acid ion having a halogen-containing functional group, and 5 mol% to 95 mol% of the total amount of isophthalic acid ions is other than fluorine at the 5-position. (It is an isophthalate ion having a halogen-containing functional group, and n represents the number of structural units consisting of AXY)
A porous polymer metal complex having the following structural unit:
(10) In formula (2), X is an isophthalic acid ion, an isophthalic acid ion having an alkyl group at the 5-position, an isophthalic acid ion having an alkoxy group at the 5-position, an isophthalic acid ion having an amino group, and a fluorine at the 5-position Isophthalic acid having two or more types of isophthalic acid ions selected from isophthalic acid ions having a halogen-containing functional group other than 5% by mole to 95% by mole of the total amount of isophthalic acid ions. The porous polymer metal complex according to (9), which is an ion.
(11) An adsorbent comprising the porous polymer metal complex according to any one of (1) to (10) above.
(12) A gas separation device using the adsorbent according to (11).
(13) A gas storage device using the adsorbent according to (11).
(14) A catalyst comprising the porous polymer metal complex according to any one of (1) to (10) above.
(15) A conductive material comprising the porous polymer metal complex according to any one of (1) to (10) above.
(16) A sensor comprising the porous polymer metal complex according to any one of (1) to (10) above.

The porous polymer metal complex of the present invention can occlude and release a large amount of gas and can perform selective gas adsorption. Moreover, the gas storage apparatus and gas separation apparatus which are accommodated inside can be manufactured using the gas storage material which consists of the porous polymer metal complex of this invention. Moreover, hydrolysis, a polymerization reaction, etc. can be catalyzed using this material.
In addition, a conductive material obtained by using this material or by doping the material with a conductive material can be formed.
Furthermore, the sensor can be formed using the present material or by doping the present material with a conductive material.

  If the porous polymer metal complex of the present invention is used, for example, as a gas separation device of a pressure swing adsorption system (hereinafter simply referred to as “PSA system”), gas can be very efficiently produced. Can be separated. In addition, the time required for the pressure change can be shortened, contributing to energy saving. Furthermore, since it can contribute to the miniaturization of the gas separation device, it is possible to increase the cost competitiveness when selling high-purity gas as a product. In addition, the cost required for the equipment that requires high purity gas can be reduced, and eventually the production cost of the final product can be reduced.

  Another application of the porous polymer metal complex of the present invention is a gas storage device. When the gas adsorbent containing the porous polymer metal complex of the present invention is applied to a gas storage device (business gas tank, consumer gas tank, vehicle fuel tank, etc.), the pressure during transportation and storage is dramatically increased. Can be reduced. As an effect resulting from the fact that the gas pressure during transportation or storage can be reduced, an improvement in the degree of freedom of shape of the gas storage device is first mentioned. In the conventional gas storage device, the gas adsorption amount cannot be maintained high unless the pressure during storage is maintained. However, in the gas storage device of the present invention, a sufficient gas adsorption amount can be maintained even if the pressure is lowered.

  When applying a gas adsorbent containing a porous polymer metal complex to a gas separation device or a gas storage device, the container shape, container material, type of gas valve, etc. need not be a special device. What is used for a gas separation apparatus or a gas storage apparatus can be used. However, improvement of various devices is not excluded, and any device is included in the scope of the present invention as long as the porous polymer metal complex of the present invention is used.

It is the figure which looked at the porous polymer metal complex of this invention from each axis on crystallography, and FIG. It is the figure which looked at the porous polymer metal complex of this invention from each axis on crystallography, and FIG. It is the figure which looked at the porous polymer metal complex of this invention from each axis on crystallography, and FIG. 1c is a c-axis projection figure. It is a figure showing the coordination structure around the metal of the porous polymer metal complex of the present invention. FIG. 3A is a diagram showing the layered state of the porous polymer metal complex of the present invention and the location of halogen atoms, and FIG. 3A is a diagram showing a linear structure cross-linked with isophthalic acid. FIG. 3B is a diagram showing a layered state of the porous polymer metal complex of the present invention and a position where a halogen atom is present, and FIG. 3B is a diagram showing a layered structure crosslinked with a bipyridine type ligand. FIG. 3c is a diagram showing the lamination mode of the porous polymer metal complex of the present invention and the location of halogen atoms, and FIG. 3c shows a two-dimensional planar laminated structure in which the layered structure shown in FIG. 3b is laminated. FIG. FIG. 4A is an a-axis projection view of another kind of porous polymer metal complex of the present invention as viewed from each crystallographic axis. It is the figure which looked at another kind of porous polymer metal complex of the present invention from each axis on the crystallography, and FIG. 4b is a b-axis projection. FIG. 4c is a c-axis projection view of another kind of porous polymer metal complex of the present invention as viewed from each crystallographic axis. It is a figure showing the coordination structure around the metal of another kind of porous polymer metal complex of the present invention. FIG. 6A is a diagram showing a lamination structure of another kind of porous polymer metal complex of the present invention and a position where a halogen atom is present, and FIG. 6A is a diagram showing an on-plane structure crosslinked with isophthalic acid. FIG. 6B is a diagram showing a stacking state of another type of porous polymer metal complex of the present invention and a position where a halogen atom is present, and FIG. 6B is a diagram showing a three-dimensional network structure crosslinked with a bipyridine type ligand. is there. FIG. 6c is a diagram showing the stacking state of another type of porous polymer metal complex of the present invention and the location of halogen atoms, and FIG. 6c is arranged so that the halogen atoms are dispersed throughout the porous polymer metal complex. FIG. It is the figure of the pattern obtained by the simulation pattern from the single-crystal X-ray data of the compound of Example 1, and a powder X-ray measurement.

  The porous polymer metal complex of the present invention is a compound represented by the following formula (1) and shown in FIG.

[AXY] _n (1)
In the formula, A represents a transition metal ion. X represents a first ligand which is an isophthalate ion having a halogen-containing functional group other than fluorine at the 5-position. Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule. n represents the number of structural units composed of AXY, and indicates that a large number of AXY are aggregated. n is a degree of polymerization showing high molecular weight, and the size is not particularly limited, but is at least 100. .

  FIGS. 1a to 1c show the crystal structure of the porous polymer metal complex of the present invention as seen from each crystallographic axis.

  FIG. 2 shows an example of the coordination structure around the transition metal ion of the porous polymer metal complex of the present invention (corresponding to the enlargement of the encircled portion in FIG. 1). The transition metal ion consists of a bipyridyl-type second ligand of two N atoms, a bidentate of the first ligand isophthalic acid carboxylic acid, and one monodentate coordination. In response to the coordination of three oxygen atoms, a five-coordinate state is obtained. However, as will be described later, a 6-coordinate structure may be formed by coordinating with a solvent or the like.

  FIG. 3 shows the three-dimensional structure of the porous polymer metal complex of the present invention. As shown in FIG. 3a, the transition metal ion forms a linear structure cross-linked with the isophthalic acid type first ligand (solid square box), and the linear structure is a bipyridine type second ligand. It is cross-linked (a part enclosed by a dotted line square) to form a planar product. This is a layered structure having a zigzag structure as shown in FIG. This layered structure is laminated as shown in FIG. 3c to form a two-dimensional planar laminated structure as a whole. The one layer shown in FIG. 3b is indicated by a solid square box in FIG. 3c. The halogen atoms are arranged so as to be dispersed throughout the porous polymer metal complex, as indicated by the circles in FIG. 3c. However, in order to make it easy to see, the circles are attached only to the two rows of halogen atoms in FIG. 3c.

Moreover, the crystal structure of another kind of porous polymer metal complex of the present invention will be described with reference to FIGS.
Figures 4a-c show views from each crystallographic axis. FIG. 5 shows the coordination structure around the transition metal ion of the porous polymer metal complex of the present invention (corresponding to the circled portion in FIG. 4). The transition metal ion consists of 2 N atoms of bipyridyl-type second ligand and 1 bidentate and 2 bidentate of isophthalic acid carboxylic acid of the first ligand for a total of 4 In response to the coordination of individual oxygen, it is in a six-coordinate state.

  As can be seen from FIG. 6a, the transition metal ion has a planar structure formed from a long square lattice crosslinked with an isophthalic acid type first ligand. Furthermore, this is bridge | crosslinked by the bipyridyl-type 2nd ligand as FIG. 6 b shows, and it has a three-dimensional network structure. As shown in FIG. 6c, the halogen atoms are arranged so as to be dispersed throughout the porous polymer metal complex.

  The porous polymer metal complex of the present invention of the two embodiments described above has isophthalic acid containing a halogen atom, one having a two-dimensional structure and the other having a difference in the three-dimensional structure and the network structure. The basic unit crosslinked by the first type ligand is further crosslinked by the bipyridyl type second ligand, and the halogen atoms are present so as to be dispersed throughout the structure. Coordination of both acidic and basic ligands to the transition metal ion results in a unique electronic state of the transition metal ion, with the presence of a halogen atom around it. One of the characteristics of the compound of the invention.

  The compound of the present invention is a bipyridyl type having a transition metal ion, an isophthalic acid type first ligand having a halogen-containing functional group other than fluorine at the 5-position, and a coordination point at both ends of the molecule. And a second ligand. What is important here is the topology of the network, and the individual bond angles do not always have the same bond angles as in FIGS. 1 to 6 because the porous polymer metal complex compound has flexibility. Depending on the synthesis solvent, drying conditions, etc., network structures may be distorted, twisted, etc., even if they have the same topology, different structural units may have different bond angles and bond distances. It is regarded as a porous polymer metal complex compound.

Since the porous polymer metal complex of the present invention is a porous body, when it comes into contact with an organic molecule such as water, alcohol or ether, it contains water or an organic solvent in the pore. For example, a complex complex represented by the formula (2) May change.
[AXY] _n (G) m (2)
In the formula, A represents a transition metal ion. X represents a first ligand which is an isophthalate ion having a halogen-containing functional group other than fluorine at the 5-position. Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule. n represents the property that a large number of structural units composed of AXY are gathered, and is a degree of polymerization showing n polymer properties, and the size is not particularly limited but is at least 100. G is an organic molecule such as water, alcohol or ether adsorbed in the pore, and m is an arbitrary number.

  However, organic molecules such as water, alcohol, and ether in these complex complexes are only weakly bonded to the porous polymer metal complex, and are removed by pretreatment such as vacuum drying when used as a gas adsorbent. Returning to the original porous polymer metal complex represented by the formula (1). Therefore, even a complex represented by the formula (2) can be regarded as essentially the same as the porous polymer metal complex of the present invention.

Moreover, the transition metal ion in the porous polymer metal complex of the present invention can be coordinated with a solvent or the like, and may be changed into a complex complex represented by, for example, formula (3).
[AXYQ _z ] _n (3)
In the formula, A represents a transition metal ion. X represents a first ligand which is an isophthalate ion having a halogen-containing functional group other than fluorine at the 5-position. Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule. n represents the property that a large number of structural units composed of AXYQ are assembled, and n is a degree of polymerization exhibiting high molecular weight, and the size is not particularly limited but is at least 100. Q represents a molecule or the like coordinated to the transition metal ion, and z is 1 or 2.

  However, Q in these complex complexes is only weakly bonded to the transition metal ion, and is removed by pretreatment such as drying under reduced pressure when used as a gas adsorbent, and is represented by the original formula (1). Returning to the porous polymer metal complex of the present invention. Therefore, even a complex represented by the formula (3) can be regarded as essentially the same as the porous polymer metal complex of the present invention.

  The porous polymer metal complex compound represented by the formula (1) of the present invention is obtained by dissolving a transition metal salt, isophthalic acid having a halogen-containing functional group other than fluorine at the 5-position and mixing in a solution state. Can be manufactured. As a solvent for dissolving the transition metal salt, good results can be obtained by using a proton solvent such as water or alcohol. Protonic solvents such as water and alcohol dissolve the transition metal salt well, and further stabilize the transition metal salt by coordinating or hydrogen bonding to the transition metal ion or counter ion. The side reaction is suppressed by suppressing the rapid reaction with the “ligand compound”. Examples of alcohols that serve as solvents include aliphatic monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, and aliphatic dihydric alcohols such as ethylene glycol. . Methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol are preferable because they are inexpensive and have high solubility of nickel salts. These alcohols may be used alone or in combination.

  As the solvent, it is also preferable to use a mixture of the above alcohols and an organic solvent other than alcohol or water. The mixing ratio is arbitrary from 1: 100 to 100: 1 (volume ratio). The mixing ratio of alcohols is preferably 30% or more from the viewpoint of improving the solubility of the transition metal salt and the ligand compound.

  As the organic solvent to be used, a highly polar solvent is preferable in terms of excellent solubility. Specifically, dialkylformamide such as tetrahydrofuran, acetonitrile, dioxane, acetone, dimethylformamide, and diethylformamide, and dialkyl such as dimethylacetamide and diethylacetamide are used. Examples include acetamide and dimethyl sulfoxide.

  A divalent transition metal salt can be used as a raw material of the transition metal ion forming the porous polymer metal complex of the present invention. Preferable examples of the divalent transition metal salt include a cobalt salt, a nickel salt, a zinc salt, and a copper salt.

  The zinc salt used in the production of the porous polymer metal complex of the present invention may be a salt containing a divalent zinc ion, and zinc nitrate and acetic acid are highly soluble in a solvent. Zinc, zinc sulfate, zinc formate, zinc chloride, and zinc bromide are preferable, and zinc nitrate and zinc sulfate are particularly preferable because of high reactivity.

  Other divalent transition metal salts such as copper salts, nickel salts and cobalt salts used in the production of the porous polymer metal complex of the present invention may be salts containing divalent transition metal ions. Nitrate, acetate, sulfate, formate, chloride and bromide are preferred because of high solubility in solvents, and nitrate and sulfate are preferred because of high reactivity with ligand compounds. A salt is particularly preferred.

Hereinafter, an isophthalate ion having a halogen-containing functional group other than fluorine at the 5-position will be described.
In the present specification, the halogen-containing functional group means a linear or branched alkyl group or alkoxy group in which H is substituted with a halogen other than fluorine. These functional groups preferably have 1 to 10 carbon atoms in that a structure in which a halogen element is dispersed in the structure is easy to form, and particularly preferably 1 to 8 in terms of excellent gas adsorbability.

  As halogen types other than fluorine, chlorine, bromine, and iodine can be raised, and bromine and iodine are preferable in that a halogen element is easily dispersed in the structure, and gas selectivity is high. Iodine is particularly preferred.

  The number of halogen atoms substituted may be a perhalogenalkyl or perhalogenalkoxy group in which H on all carbons is substituted with halogen, or a monohalogenalkyl group or monohalogen in which only one H on carbon is substituted with halogen. An alkoxy group can be illustrated. In the case of a monohalogenalkyl or monohalogenalkoxy group, a monohalogenalkyl group or monohalogenalkoxy group in which a halogen is substituted at the terminal is particularly preferred in order to ensure flexibility of the alkyl group or alkoxy group.

  In a porous polymer metal complex containing at least one isophthalic acid ligand having a halogen-containing functional group other than fluorine at the 5-position of the benzene ring and a bipyridyl type second ligand, a plurality of types of isophthalates are used as raw materials. It has been confirmed that it is possible to form a so-called solid solution type porous polymer metal complex, which is a porous polymer metal complex containing a plurality of types of isophthalic acids, by mixing acids. At this time, at least one of the plural types of isophthalic acids to be used in combination must be isophthalic acids having a halogen-containing functional group other than fluorine at the 5-position, and the content of this is the total amount of isophthalic acid ions. It is 5 mol%-95 mol% with respect to it, Preferably it is 20%-80 mol%.

This solid solution type porous polymer metal complex is a compound represented by the following formula (4) and shown in FIGS.
[AXY] _n (4)
In the formula, A represents a transition metal ion, and X represents a first ligand having a plurality of types of isophthalate ions including at least one isophthalate ion having a halogen-containing functional group other than fluorine at the 5-position. Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule. n represents the property that a large number of structural units composed of AXY are gathered, and is a polymerization degree exhibiting n polymer properties, and the size is not particularly limited, but is at least 100.

  Isophthalic acid first coordination comprising transition metal ion, bipyridyl-type second ligand having coordination points at both ends of the molecule, and isophthalic acid ion or isophthalic acid ion having a substituent at the 5-position It has been confirmed that when two or more kinds of children are combined, the solid solution type porous polymer metal complex shown in FIGS. The solid solution type porous polymer metal complex of the present invention comprises at least an isophthalate ion and an isophthalate ion having a substituent at the 5-position in the solid solution-type porous polymer metal complex. The isophthalic acid ion having a halogen functional group is contained in an amount of 5 mol% or more of the total amount of isophthalic acid ions. A plurality of types of isophthalic acid used in combination may include isophthalic acid having a halogen-containing functional group other than fluorine at the 5-position and isophthalic acid having a halogen-containing functional group other than fluorine at another 5-position.

The isophthalate ion used in the solid solution type porous polymer metal complex of the present invention is an isophthalate ion having a substituent at the 5-position of the benzene ring in addition to the isophthalic acid having a halogen-containing functional group other than fluorine at the 5-position. Can be included. Examples of substituents at the 5-position include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, aralkyl groups, substituted or unsubstituted amino groups, nitro groups, amide groups, and formyl And a group selected from a group, a carbonyl group, an ester group, an azide group, a carboxyl group, a sulfo group, a hydroxyl group and the like.
As the alkyl group, an alkyl group having 1 to 12 carbon atoms such as a methyl group or an ethyl group, particularly an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the substituted alkyl group include a hydroxy group and an amino group.
As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms, particularly 1 to 6 alkoxy groups, particularly a methoxy group, an ethoxy group, and a benzyloxy group are preferable. Examples of the substituent for the substituted alkoxy group include a hydroxy group, an amino group, and a dimethylamino group.
As the aryl group, a phenyl group and a parahydroxyphenyl group are preferable. Examples of the substituted aryl group include a parahydroxyphenyl group and a paradimethylaminophenyl group.
As the aralkyl group, a benzyl group or a phenyl group in which one or more of o-, m-, and p- are substituted with a methyl group and / or an ethyl group is preferable.
A substituted or unsubstituted amino group is preferable, and specifically, an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, and a diphenylamino group are more preferable.

  A combination of an isophthalic acid ion having a halogen-containing functional group other than fluorine at the 5-position, an isophthalic acid ion, and an isophthalic acid ion having an amino group, an alkyl group, or an alkoxy group at the 5-position is preferable.

  In the case of this solid solution type porous polymer metal complex, X is two or more kinds of isophthalate ion ligands, and can be, for example, three kinds or four kinds. Although there is no upper limit, in general, up to 4 isophthalate ions are preferable in order to prevent the adsorption characteristics from being lowered by the interaction of functional groups of many different types of isophthalate ions.

  Next, the second ligand that forms the porous polymer metal complex of the present invention will be described. A 2nd ligand is a linear molecule | numerator, Comprising: It is a bidentate ligand which has the nitrogen atom used as a coordination point in the both ends.

  The second ligand that can be preferably used in the present invention is a pyrazine, bipyridine, or a bipyridine analog having a 4-pyridyl group at both ends of the molecule.

  The bipyridine is preferably a bipyridine isomer such as 4,4'-bipyridine, 3,4'-bipyridine, or 3,3'-bipyridine.

  Examples of the bipyridine analog having a 4-pyridyl group at both ends of the molecule that can be preferably used in the present invention include compounds represented by the following general formula.

In the formula, R is a C1-C4 alkyl group, a C2-C4 alkylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, or a diazo bond,

Represents. X represents -S-, -O-, or -NH-. Y represents an arylene group.

  The second ligand used in the present invention is preferably pyrazine, bipyridine, or R in the above chemical formula, a diazene-1,2-diyl group, an ethylene group, a vinylene group, an ethynylene group, because of the stability of the compound used. Thiophene-2,5-diyl group, 9H-fluorene-2,7-diyl group, naphthalene-1,4-dii group, biphenyl-1,4-diyl group, phenylene group (more preferably p-phenylene group), It is a bipyridine-related compound which is a 1,2,4,5-tetrazine-1,4-diyl group or a 4,4′-biphenylene group.

  Specifically, the second ligand used in the present invention is pyrazine, 4,4′-bipyridine, 3,4′-bipyridine, 3,3′-bipyridine containing two aromatic rings, (E) -4,4 '-(ethylene-1,2-diyl) bipyridine, 4,4'-(diazene-1,2-diyl) bibipyridine, N- (pyridin-4-yl) isonicotinamide, (E)- 4,4 ′-(1,4-) containing three or more aromatic rings, such as 4,4 ′-(ethene-1,2-diyl) bipyridine, 4,4 ′-(ethyne-1,2-diyl) bipyridine Phenylene) bipyridine, 3,6-bi (pyridin-4-yl) -1,2,4,5-tetrazine, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 1, 4-bis (4-pyridyl) benzene, 4,4 ′-(naphthalene-1,4-diylbis ( Chin-2,1-diyl) bipyridine, 4,4 ′-(9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bipyridine, etc. Among these, pyrazine, 4, 4'-bipyridyl, 4,4 '-(1,4-phenylene) bipyridine, (E) -4,4'-(ethyne-1,2-diyl) bipyridine, 3,6-di (4-pyridyl)- 1,2,4,5-tetrazine and 1,4-bis (4-pyridyl) benzene are preferred.

  The second ligand may have a substituent on the aromatic ring. As the kind of the substituent, an alkyl group such as methyl, an alkyl group having a polar functional group such as hydroxymethyl group, or an amino group such as dimethylamino group is preferable. It is.

  In the method for producing a porous polymer metal complex of the present invention, a base can be added as a reaction accelerator. Examples of the base include, for example, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like as inorganic bases. Examples of the organic base include triethylamine, diethylisopropylamine, pyridine, 2,6-lutidine and the like. Lithium hydroxide, sodium carbonate, sodium hydroxide, and pyridine are preferred because of their high reaction acceleration. The addition amount of the reaction accelerator is preferably 0.1 to 6.0 mol, and the side reaction is small in that the acceleration effect of the reaction is remarkable with respect to the total molar amount of isophthalic acid used in the reaction. More preferably, it is 0.5-4.0 mol.

  In the reaction of the transition metal salt solution with the ligand compound, the transition metal salt and the ligand compound are separately added in addition to the method of adding the solvent after the transition metal salt and the ligand compound are loaded into the container. These solutions may be mixed after preparing as a solution. The solution may be mixed by adding the ligand compound solution to the transition metal salt solution or vice versa. In addition, as a mixing method, it is not always necessary to mix the solutions, for example, a method in which a solid ligand compound is added to a transition metal salt solution and a solvent is simultaneously added, or a transition metal salt is charged in a reaction vessel. Various methods can be used as long as the reaction finally occurs substantially in the solvent, such as injecting a solid or solution of the ligand compound and then injecting a solvent for dissolving the transition metal salt. Is possible. However, the method of dropping and mixing the transition metal salt solution and the ligand compound solution is industrially the most convenient and preferable.

  The concentration of the solution to be mixed is 40 mmol / L to 4 mol / L, preferably 80 mmol / L to 2 mol / L for the transition metal salt solution. The organic solvent solution of the ligand compound is 40 mmol / L to 3 mol / L, preferably 80 mmol / L to 1.8 mol / L. Even if the reaction is carried out at a concentration lower than the lower limit, the target product can be obtained, but this is not preferable because the production efficiency is lowered. A concentration higher than the upper limit is not preferable because the adsorptivity decreases.

  The reaction temperature is -20 to 180 ° C, preferably 25 to 140 ° C. If carried out at a low temperature of less than -20 ° C, the solubility of the raw material is lowered, which is not preferable. Although it is possible to carry out the reaction at a temperature higher than 180 ° C. using an autoclave or the like, there is no substantial meaning because the yield is not improved for the energy cost such as heating.

  The mixing ratio of the transition metal salt and the organic ligand compound used in the reaction of the present invention is within a range of 3: 1 to 1: 5, preferably 1.5: 1 to 1: 3. is there. In a range other than the molar ratio of 3: 1 to 1: 5, the yield of the target product decreases, and unreacted raw materials remain, making it difficult to take out the target product.

  In the reaction between the transition metal salt and the organic ligand compound, it is important that a trace amount of halogen salt is allowed to coexist in the reaction system. As the kind of halogen element, chlorine, bromine and iodine are preferable, and chlorine and bromine are preferable because they are effective in a small amount. As the counter ion of the halogen ion, sodium, potassium, rubidium and the like are preferable, but sodium and potassium are preferable because they are effective in a small amount. The added amount of the halogen salt is preferably 0.0001 mol% to 0.01 mol% and 0.0005 mol% to 0.005 mol% from the viewpoint of improving the yield with respect to the ligand compound. The coexistence of such a trace amount of halogen salts has a halogen-containing functional group other than fluorine when an isophthalic acid ligand compound having a halogen-containing functional group other than fluorine is used as the ligand compound at the 5-position. This has the effect of preventing the yield reduction that is likely to occur when no isophthalic acid ligand compound is used. The effect of adding a trace amount of halogen salts is that when an isophthalic acid ligand compound having a halogen-containing functional group other than fluorine at the 5-position is used in the reaction, a transition metal ion and a halogen-containing functional group other than fluorine at the 5-position are added. Interaction with the halogen atom of the isophthalic acid ligand possessed creates a cluster, thereby inhibiting the reaction. However, when a small amount of halogen salt is present, this is a transition metal ion and a halogen-containing functional group other than fluorine at the 5-position. It is presumed that the reaction is promoted by suppressing the interaction with the isophthalic acid ligand having a group. However, the scope of the present invention is not limited to this estimation.

  The reaction between the transition metal salt and the organic ligand compound can be carried out using an ordinary glass-lined SUS reaction vessel and a mechanical stirrer. After completion of the reaction, the target substance and the raw material can be separated by filtration and drying to produce a target substance with high purity.

  A ligand having a monohalogenated alkyloxy substituent can be obtained by condensation of α-bromo-ω-chloroalkane with phenol to give a chloro-substituted product. The bromine-substituted product and iodine-substituted product can be reacted with sodium bromide, sodium iodide and the like to obtain the target ligand. A ligand having perhalogenalkyl or perhalogenalkoxy can be obtained by acting a halogenating agent such as N-bromosuccinimide.

Whether or not the porous polymer metal complex obtained by the above reaction has the target structure can be confirmed by analyzing the reflection obtained by single crystal X-ray crystal analysis. It can also be confirmed by the reflection pattern of powder X-ray analysis.
Whether or not the porous polymer metal complex obtained by the above reaction is porous can be confirmed by thermogravimetric analysis (TG). For example, in a nitrogen atmosphere (flow rate = 50 mL / min), it can be confirmed whether the weight loss from the temperature range of room temperature to 200 ° C. is 3 to 50% by measuring the heating rate = 5 ° C./min. The gas adsorption ability of the porous polymer metal complex obtained by the above reaction can be measured using a commercially available gas adsorption apparatus.

[Combination of adsorbent containing porous polymer metal complex]
The gas adsorbent containing the porous polymer metal complex of the present invention (hereinafter simply referred to as “adsorbent (A)”) may be used alone as an adsorbent, or may be used in combination with other adsorbents. May be. When used in combination, as another adsorbent, a gas adsorbent having very excellent adsorption characteristics when used in combination with an adsorbent (B) that exhibits a behavior in which the adsorption isotherm coincides with the desorption isotherm. It can be.

  Here, the adsorbent (B) is a material that exhibits a behavior in which an adsorption isotherm and a desorption isotherm relating to gas coincide with each other. That is, as shown in FIG. 7, the gas pressure-gas adsorption amount curve at the time of adsorption is substantially the same as the gas pressure-gas adsorption amount curve at the time of desorption. The adsorbent (B) is not particularly limited as long as it is a material having such characteristics, and a physical adsorbent, a chemical adsorbent, and a physicochemical adsorbent formed by combining these adsorbents (B) are used. Can be used as

  A physical adsorbent refers to an adsorbent that adsorbs molecules to be adsorbed using weak force such as interaction between molecules. Examples of the physical adsorbent include activated carbon, silica gel, activated alumina, zeolite, clay, super adsorbent fiber, and metal complex. A chemical adsorbent refers to an adsorbent that adsorbs molecules to be adsorbed by chemical bonds. Examples of the chemical adsorbent include calcium carbonate, calcium sulfate, potassium permanganate, sodium carbonate, potassium carbonate, sodium phosphate, and activated metal. The physicochemical adsorbent refers to an adsorbent that has an adsorption mechanism for both the physical adsorbent and the chemical adsorbent. Two or more of these may be combined and used as the adsorbent (B). However, the technical scope of the present invention is not limited to these specific examples. The shape of the adsorbent (B) is not particularly limited, but generally a powdery material having an average particle size of 500 to 5000 μm can be used.

As the adsorbent (B), activated carbon is preferable in consideration of production cost and gas adsorption performance. Activated carbon is relatively inexpensive and has a large amount of gas adsorption per mass. In addition, activated carbon has poor cycle characteristics related to gas adsorption and desorption, and when adsorption and desorption is repeated, the amount of gas adsorption tends to be remarkably reduced. For this reason, in the past, it was difficult to use in gas storage devices and gas separation devices despite the large amount of gas adsorption per mass. In this regard, when used as the adsorbent (B) in the composite of the adsorbent (A) of the present invention, the excellent gas adsorption performance of the activated carbon can be sufficiently derived. Moreover, since the activated carbon has a tendency that the amount of adsorption increases as the specific surface area increases, the specific surface area of the activated carbon is preferably 1000 m ² / g or more.

  Moreover, it is preferable that the structure of the adsorbent (B) to be used is appropriately controlled according to the gas to be adsorbed. For example, the pores contained in the activated carbon can be classified into super micropores (up to 0.8 nm), micropores (0.8 to 2 nm), mesopores (2 to 50 nm), and macropores (50 nm to) depending on the size of the pores. . Gases that are easily adsorbed differ depending on the size of the pores, and methane gas is easily adsorbed to micropores. Therefore, when it is desired to adsorb methane gas, the pore distribution of the activated carbon may be controlled so that the proportion of micropores is increased.

  When the adsorbent (A) and adsorbent (B) of the present invention are combined, the adsorbent (A) covers the adsorbent (B), but there is no crack or incomplete coating, and the adsorbent It is preferable that (B) is completely covered with the adsorbent (A) so as not to touch the outside air. However, even if there are some cracks or the like in the adsorbent (A), the adsorbent (B) can inhibit free gas adsorption, and the adsorbent (B) covered with the adsorbent (A). If it shows gas adsorption characteristics similar to those of the adsorbent (A) with regard to gas adsorption, it is included in the scope of the present invention. Preferably, the adsorbent (B) is covered with 5 to 50% by volume of the adsorbent (A) with respect to the adsorbent (B). Further, the thickness of the adsorbent (A) covering the adsorbent (B) is determined according to the type of the adsorbent (A), but if the adsorbent (A) is too thin, the gas to the adsorbent (B) There is a possibility that the adsorption characteristics cannot be controlled sufficiently. On the other hand, if the adsorbent (A) is too thick, gas adsorption to the adsorbent (B) is difficult to occur, and the gas adsorption amount as a whole may be reduced. Considering these, the average thickness of the adsorbent (A) is preferably 10 to 100 μm. The thickness of the adsorbent (A) can be controlled by adjusting the amount of adsorbent (A) used. The thickness of the adsorbent (A) can be calculated from a cross-sectional photograph taken using an electron microscope.

  As a method of combining the adsorbent (A) and the adsorbent (B), (1) the adsorbent (B) that does not dissolve in the solution is added to the solution in which the adsorbent (A) is dissolved. Then, a method of adsorbing the adsorbent (A) on the surface of the adsorbent (B) by crystal growth of the adsorbent (A), (2) preparing a slurry containing the adsorbent (A), A method of attaching the adsorbent (A) to the surface of the adsorbent (B) by coating the surface of the adsorbent (B) and drying can be used.

  The porous polymer metal complex compound of the present invention is porous so that a substance can enter and exit, and has an electrically positive cation, a negative carboxyl group, and a polarized halogen-substituted functional group. Therefore, it can be used as various catalytic reactions. Since the pores of the porous polymer metal complex are at the nano level, and the incorporated substance has a very high probability of collision with the pore walls, the reaction with the catalytic active sites as described above is efficient. Since it is performed, it can be used as a catalyst. Specifically, it can be used for synthesis of esters or the like, decomposition catalysts, methanol synthesis catalysts from synthesis gas, various reactions catalyzed by Lewis acids, bases and the like such as aldol reaction.

  The porous polymer metal complex compound of the present invention is porous so that a substance can enter and exit, and has an electrically positive cation, a negative carboxyl group, and a polarized halogen-substituted functional group. In addition, because it has nano-level pores, even when the concentration of various substances is low, these molecules can be efficiently incorporated to change color, change conductivity, change structure, etc. Therefore, it can be used as a gas sensor such as carbon monoxide and nitric oxide, or as an organic vapor sensor such as aromatic.

  The porous polymer metal complex compound of the present invention has a porosity that allows a substance to enter and exit. For this reason, by introducing a conductive substance such as imidazole into the pores, imidazole molecules are close to each other and can exhibit high conductivity, and therefore can be used as a conductive material. is there.

  The method for preparing the porous polymer metal complex of the present invention has various conditions and cannot be determined uniquely. Here, one condition will be described as an example.

Example 1
0.02 mmol of zinc sulfate, water (2 mL) in which 0.001 micromol of sodium chloride was dissolved, 0.02 mmol of 5- (3-iodo-n-propyloxy) isophthalic acid, and 4,4′-bipyridine 0 Methanol (2 mL) in which 0.02 mmol was dissolved was slowly layered and allowed to stand at 25 ° C. for one week to obtain colorless single crystals. After a single crystal having a diameter of about 170 microns was coated with Palaton so as not to be exposed to the atmosphere, a single crystal measuring device manufactured by Rigaku Co., Ltd. (single crystal structure analyzer VariMax for ultrafine crystals, MoKα ray (λ = 0. 71069 Å)) (irradiation time 16 seconds, d = 45 mm, 2θ = −20, temperature = −180 ° C.). The obtained diffraction image was analyzed using analysis software “hermit crab XG2009”, and it was confirmed that it had a structure as shown in FIGS. 1 to 3 (a = 15.098 (2), b = 19.369 (3), c = 27.787 (3); α = 90, β = 90, γ = 90; space group = Pbca)).

  Further, 1 mmol of copper chloride dihydrate, 0.05 μmol of sodium chloride, 1 mmol of 5- (3-iodo-n-propyloxy) isophthalic acid, and 1 mmol of 4,4′-bipyridine were added to methanol (20 mL). And the container was sealed and heated at 120 ° C. for 1 hour. After cooling, it was filtered and washed with methanol to obtain 109 mg of white powder. The result of measuring this powder with a powder X-ray apparatus DISCOVER D8 with GADDS manufactured by Bruker AX Co., Ltd. (CuKα (λ = 1.54Å), 2θ = 4-40, measured at room temperature), reflection pattern shown in FIG. Which was identical to the single crystal powder simulation pattern described above. That is, it was confirmed that a porous polymer metal complex having the same structure could be synthesized by the above two kinds of the present methods, and that it could be analyzed by single crystal X-ray diffraction and powder X-ray diffraction methods.

Examples 2-11
In the same manner as in Example 1, synthesis was performed using the raw materials shown in Table 1.

Example 12
0.1 mmol of zinc sulfate, 0.01 μmol of 5- (3-iodo-n-propyloxy) isophthalic acid and 0.001 μmol of sodium chloride were dissolved in 8 mL of ethanol, and 4,4′-bipyridine 0 Slowly layer on 8 mL of ethanol with 1 mmol dissolved. By holding this at 10 degrees, a colorless single crystal was obtained. After a single crystal having a diameter of about 110 microns was coated with Palaton so as not to be exposed to the atmosphere, a single crystal measuring device manufactured by Rigaku Co., Ltd. (single crystal structure analysis device VariMax for ultrafine crystal, MoKα ray (λ = 0. 71069Å)) (irradiation time 12 seconds, d = 45 mm, 2θ = −20, temperature = −180 ° C.), and the obtained diffraction image was analyzed using analysis software “hermit crab XG2009” As shown in FIGS. 4-6, it confirmed that it has a three-dimensional network structure (a = 15.7696 (17), b = 16.22978 (18), c = 11.4149 (11); α = 90, β = 90, γ = 90; space group = P212121)).

Examples 13-15
In the same manner as in Example 12, synthesis was performed using the raw materials shown in Table 2.

Examples 16-19
In the same manner as in Example 1, synthesis was performed using the raw materials shown in Table 3. The difference between Examples 16 to 19 and Example 1 is that, in Example 1, there is one kind of isophthalic acid derivative as the first ligand, but in Examples 16 to 19, Table 3 as the first ligand. As shown in Fig. 2, a solid solution is synthesized using a mixture of two types of ligands (A, B).

Comparative Examples 1 and 2
In the same manner as in Example 1, a porous polymer metal complex in which a substituent having no halogen element was substituted at the 5-position of isophthalic acid was synthesized (Table 4).

Comparative Examples 3-5
In the same manner as in Examples 16 to 19, a solid solution was synthesized using a mixture of two kinds of ligands (A, B) (Table 5). However, the synthesis was carried out with the ratio of the ligand B having no halogen element being higher than that in Examples 16-19.

<Results of gas adsorption>
Various gas adsorption characteristics of the obtained gas adsorbent were measured at various temperatures. A BET automatic adsorption device (Bell Mini II manufactured by Nippon Bell Co., Ltd.) was used. Prior to the measurement, the sample was vacuum-dried at 393 K for 6 hours to remove solvent molecules that may remain in a trace amount.

  Tables 1 to 5 show the amounts of adsorption of various gases at various temperatures. In all of Tables 1 to 5, the adsorption amount is an adsorption amount at a relative pressure of 0.95, and the relative pressure is a value obtained by dividing the pressure at the time of adsorption by the boiling point of the gas at the temperature. .

  At any temperature, the adsorbent containing a porous polymer metal complex using isophthalic acid having a halogen-containing functional group other than fluorine at the 5-position of the present invention has an oxygen gas adsorption amount different from that of other gases. Many compared. Further, the adsorption ratio of carbon monoxide and nitrogen (carbon monoxide adsorption amount / nitrogen adsorption amount at 273K) is large, and it is found that it is advantageous for separation of carbon monoxide and nitrogen, which are usually difficult to separate. The effect is clear when compared with the adsorbent containing the porous polymer metal complex using isophthalic acid in which the functional group at the 5-position of Comparative Examples 1 and 2 does not contain a halogen atom.

  In the porous polymer metal complex of the present invention, a large number of micropores formed by alignment of ligands are present in the substance. Utilizing this porosity, oxygen, carbon monoxide can be selectively adsorbed, separated and stored.

Claims (16)

[AXY] _n (1)
(In the formula, A represents a transition metal ion, X represents a first ligand which is an isophthalic acid ion having a halogen-containing functional group other than fluorine at the 5-position, and Y represents a coordination point at both ends of the molecule. Represents a bipyridyl-type second ligand possessed, and n represents the number of structural units comprising AXY)
A porous polymer metal complex having the following structural unit:   The porous polymer metal complex according to claim 1, wherein the transition metal ion is any one of a cobalt ion, a nickel ion, a copper ion, and a zinc ion.   The porous polymer metal complex according to claim 1, wherein the transition metal ion is a zinc ion.   The porous polymer metal complex according to claim 1 or 2, wherein the halogen element of the halogen-containing functional group is chlorine, bromine, or iodine.   The porous polymer metal complex according to claim 1, wherein the halogen element of the halogen-containing functional group is iodine.   The porous polymer metal complex according to claim 1, wherein the halogen-containing functional group is a linear or branched alkyl group or alkoxy group containing a halogen element.   The porous polymer metal complex according to claim 1, wherein the halogen-containing functional group is a linear or branched alkyl group or alkoxy group having 1 to 10 carbon atoms.   The porous polymer metal complex according to any one of claims 1 to 7, wherein the halogen-containing functional group contains 1 to 21 halogen atoms. [AXY] _n (2)
(In the formula, A represents a transition metal ion, Y represents a bipyridyl-type second ligand having coordination points at both ends of the molecule, and X represents an isophthalate ion or other than fluorine at the 5-position. This represents the first ligand which is a plurality of types of isophthalate ions containing at least one isophthalate ion having a halogen-containing functional group, and 5 mol% to 95 mol% of the total amount of isophthalate ions is other than fluorine at the 5-position. (It is an isophthalate ion having a halogen-containing functional group, and n represents the number of structural units consisting of AXY)
A porous polymer metal complex having the following structural unit:   In the formula (2), X is an isophthalic acid ion, an isophthalic acid ion having an alkyl group at the 5th position, an isophthalic acid ion having an alkoxy group at the 5th position, an isophthalic acid ion having an amino group, and a non-fluorine content at the 5th position. Two or more types of isophthalic acid ions selected from isophthalic acid ions having a halogen functional group, and 5 mol% to 95 mol% of the total amount of isophthalic acid ions are isophthalic acid ions having a halogen-containing functional group at the 5-position The porous polymer metal complex according to claim 9.   An adsorbent comprising the porous polymer metal complex according to claim 1.   A gas separation device using the adsorbent according to claim 11.   A gas storage device using the adsorbent according to claim 11.   The catalyst containing the porous polymeric metal complex in any one of Claims 1-10.   The electroconductive material containing the porous polymer metal complex in any one of Claims 1-10.   A sensor comprising the porous polymer metal complex according to claim 1.