JP5013173B2 - Organometallic complex, occlusion material and catalyst using the same - Google Patents

Description

  The present invention relates to an organometallic complex, and an occlusion material and catalyst using the same.

  Conventionally, various organometallic complexes that can be used as storage materials and catalysts have been reported (for example, Tomohiko Sato. Et al., Microporous Rhodium (II) 4, 4 ′, 4 ″, 4 ′ ″). -(21H, 23H-porphin-5,10,15,20-tetrayl) tetrakisbenzoate., Chemistry Letter, published in 2003, Vol. et al., Novel microporous rhodium (II) carbohydrate polymer complexes consolidating metallophyrin., Journal of Ca. Alysis, published 2005, Vol.232, reference P186-P198 (Non-Patent Document 2)).

  As such an organometallic complex, for example, in Japanese Patent Application Laid-Open No. 2004-238347 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2004-67596 (Patent Document 2), a metal atom and a metal coordinated to the metal atom are disclosed. An organometallic complex having a specific two-dimensional lattice structure consisting of a ligand having a porphyrin structure as a repeating unit is disclosed. Further, in JP-A-2000-63385 (Patent Document 3), a specific dicarboxylic acid is disclosed. A dicarboxylic acid metal complex is disclosed in which an acid is coordinated to at least one divalent metal ion selected from copper, chromium, molybdenum, rhodium, palladium and tungsten.

However, the conventional organometallic complexes having a porphyrin structure have not yet sufficient storage characteristics and catalytic action.
JP 2004-238347 A Japanese Patent Laid-Open No. 2004-67596 JP 2000-63385 A Tomohiko Sato. et al. , Microporous Rhodium (II) 4, 4 ′, 4 ″, 4 ′ ″-(21H, 23H- porphin-5, 10, 15, 20-tetrayl) tetrakisbenzoate. , Chemistry Letter, published 2003, Vol. 32, no. 9, p854-p855 Tomohiko Sato. et al. , Novel microporous rhodium (II) carboxylate polymer complexes containing metallophyrin. , Journal of Catalysis, 2005, Vol. 232, p186-p198

  The present invention has been made in view of the above-described problems of the prior art, and is an organometallic complex having a porphyrin structure, which can exhibit high occlusion characteristics and excellent catalytic action. And an occlusion substance and a catalyst using the same.

  As a result of intensive studies to achieve the above object, the present inventors have achieved a high level of occlusion characteristics and an excellent catalyst by using an organometallic complex in which a specific porphyrin derivative is bound via a specific carboxylic acid metal complex. The present inventors have found that an organometallic complex having a porphyrin structure capable of exhibiting an action can be obtained, and the present invention has been completed.

  That is, the organometallic complex of the present invention has the following general formula (1):

Wherein (1), M ¹ is either indicates a metal atom coordinated to a nitrogen atom, or indicate two hydrogen atoms attached to the nitrogen atom, R ¹ to R ⁸ Waso respectively Indicates a hydrogen atom . ]
A porphyrin derivative represented by the following general formula (2):

[In Formula (2), R ⁹ may be the same or different, each represents a monovalent organic substituent selected from the group consisting of an alkyl group and an aryl group , and M ² may be the same or different. , Each represents a metal atom. ]
Is coupled in via the carboxylic acid metal complex represented,
The following general formula (3):
Wherein (3), ^{M 1} may be the same or different, have the same meanings as ^{M 1} in the general formula ^{(1), R 1} of R 1 to R ⁸ are in the general formula (1) to R ⁸ in the above formula, X is illustrates a carboxylic acid metal complex represented by the general formula (2). ]
Having a two-dimensional lattice structure represented by
It is characterized by.

In the organometallic complex of the present invention, M ¹ in the general formula (1) is a group consisting of copper, ruthenium, rhodium, molybdenum, zinc, titanium, vanadium, aluminum, magnesium, cerium, tungsten, rhenium and iron. It is preferably a metal atom selected from or two hydrogen atoms.

In the organometallic complex of the present invention, M ² in the general formula (2) is selected from the group consisting of copper, ruthenium, rhodium, molybdenum, chromium, zinc, tungsten, rhenium, technetium and iron, respectively. It is preferably a metal atom that can form a binuclear structure.

  The organometallic complex of the present invention preferably has a maximum pore diameter of 0.6 to 2.5 nm among a plurality of pores having different diameters in the repeating unit of the two-dimensional lattice structure.

  The occlusion material of the present invention contains the organometallic complex of the present invention.

  Furthermore, the catalyst of the present invention is characterized by containing the organometallic complex of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the organometallic complex which has a porphyrin structure which can exhibit a high occlusion characteristic and the outstanding catalytic action, and an occlusion substance and a catalyst using the same.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the organometallic complex of the present invention will be described. That is, the organometallic complex of the present invention has the following general formula (1):

[In formula (1), M ¹ represents a metal atom coordinated to a nitrogen atom, or two hydrogen atoms bonded to the nitrogen atom, and R ^{1 to} R ⁸ are the same or different. And each represents a monovalent substituent. ]
A porphyrin derivative represented by the following general formula (2):

[In Formula (2), R ⁹ may be the same or different and each represents a monovalent organic substituent, M ² may be the same or different, and each represents a metal atom. ]
It couple | bonds through the carboxylic acid metal complex represented by these.

M ¹ in the porphyrin derivative according to the present invention is a metal atom coordinated to a nitrogen atom or two hydrogen atoms bonded to the nitrogen atom. When M ¹ is two hydrogen atoms bonded to a nitrogen atom, the porphyrin derivative is represented by the following general formula (4):

It has a structure represented by.

As described above, M ¹ represents two hydrogen atoms or metal atoms. The metal atom that can be selected as M ¹ is not particularly limited as long as the nitrogen atom inside the porphyrin ring can be coordinated, and copper, ruthenium, rhodium, molybdenum, zinc, Tungsten, rhenium, iron, cerium, magnesium, aluminum, titanium, vanadium, silicon, calcium, manganese, cobalt, nickel, gallium, germanium, zirconium, niobium, technetium, palladium, silver, cadmium, indium, tin, antimony, osmium, Examples include iridium. Examples of the metal atom that can be selected as M ¹ include copper, ruthenium, rhodium, molybdenum, zinc, titanium, vanadium, aluminum, magnesium, from the viewpoint of stability and toxicity of the compound having high coordination ability. A metal atom selected from the group consisting of cerium, tungsten, rhenium and iron is preferred. Further, as M ¹ , copper is more preferable from the viewpoint of ease of production, and rhodium, ruthenium, titanium, iron, and cerium are more preferable from the viewpoint of further improving the catalytic ability.

Moreover, R < ¹ > -R < ⁸ > in the porphyrin derivative concerning this invention may be same or different, and each is a monovalent substituent. Although it does not restrict | limit especially as such a monovalent substituent, From a viewpoint of a steric hindrance and the electron density of a pyrrole ring, a hydrogen atom, a halogen atom, a nitro group, a silyl group, a cyano group, a sulfonic acid group, a mercapto group, an alkyl A monovalent substituent selected from the group consisting of a group, a halogenated alkyl group, an aryl group and a halogenated aryl group is preferred, and among them, a hydrogen atom and a methyl group are more preferred.

In addition, examples of the halogen atom that can be selected as R ^{1 to} R ⁸ include fluorine, chlorine, bromine, iodine, and the like, among which fluorine and chlorine are preferable.

The alkyl group, the halogenated alkyl group, the aryl group, and the halogenated aryl group that can be selected as R ^{1 to} R ⁸ are those having 1 to 12 carbon atoms (more preferably 1 to 6). Among these, a methyl group and a trifluoromethyl group are particularly preferable from the viewpoint of bulkiness of the substituent in order not to reduce the pore volume.

  Moreover, the carboxylic acid metal complex concerning this invention is a carboxylic acid metal complex represented by the said General formula (2).

R ⁹ in the carboxylic acid metal complex according to the present invention may be the same or different, and each is a monovalent organic substituent. The monovalent organic substituent that can be selected as R ⁹ is not particularly limited, but from the viewpoint of ease of synthesis, for example, solubility in a solvent, a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group. And a halogenated aryl group are preferable, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, a tolyl group, a naphthyl group, a cyclohexyl group, an anthryl group or a pyrenyl group are more preferable, and among them, a methyl group, a phenyl group Is particularly preferred.

M ² in the carboxylic acid metal complex according to the present invention is a metal atom. The metal atom that can be selected as M ² is not particularly limited as long as it is a metal atom that can form a binuclear structure. For example, copper, ruthenium, rhodium, molybdenum, chromium, zinc, tungsten, rhenium, technetium, Examples thereof include iron, magnesium, aluminum, silicon, calcium, titanium, vanadium, manganese, cobalt, nickel, gallium, germanium, zirconium, niobium, palladium, silver, cadmium, indium, tin, antimony, osmium, and iridium.

The metal atom that can be selected as M ² is preferably copper, ruthenium, rhodium, molybdenum, chromium, zinc, tungsten, rhenium, technetium, or iron from the viewpoint of the strength of coordination ability between the carboxylic acid and the metal. Of these, copper, ruthenium, rhodium or zinc is more preferable.

  Moreover, as an organometallic complex of this invention, following General formula (3):

Wherein (3), ^{M 1} may be the same or different, have the same meanings as ^{M 1} in the general formula ^{(1), R 1} of R 1 to R ⁸ are in the general formula (1) to R ⁸ in the above formula, X is illustrates a carboxylic acid metal complex represented by the general formula (2). ]
It is preferable to have a two-dimensional lattice structure represented by By having such a two-dimensional lattice structure as a repeating unit, the pore diameter of the pores of the organometallic complex becomes larger, and the occlusion ability and catalytic ability tend to be further improved. Here, the pore referred to in the present invention means a pore formed when the two-dimensional lattice structure represented by the general formula (3) is laminated by a self-integrating function, and the pore diameter is an atomic van der. The maximum distance in a space where no other atom or molecule exists when the Wales radius is considered.

  Further, as the organometallic complex of the present invention, it is preferable that the pore diameter of the largest pore among the plurality of pores having different diameters of the repeating unit of the two-dimensional lattice structure is 0.6 to 2.5 nm. 1.0 to 2.5 nm is more preferable. If the pore diameter is less than the lower limit, the pore diameter tends to be too small to exhibit sufficient occlusion ability and catalytic ability. On the other hand, if the pore diameter exceeds the upper limit, the pore tends to be recognized as a space that is difficult to adsorb molecules. It is in.

Moreover, in the organometallic complex of this invention, although there is no restriction | limiting in particular about the specific surface area, it is preferable that it is 30 m < ² > / g or more, and it is more preferable that it is 100 m < ² > / g or more. If the specific surface area is less than the lower limit, sufficient occlusion ability and catalytic ability tend not to be exhibited. Such a specific surface area can be calculated from the adsorption isotherm using the BET isotherm adsorption equation and the Langmuir adsorption isotherm equation.

In addition, the pore volume is preferably 0.01 cm ³ / g or more, and more preferably 0.1 cm ³ / g or more. If the pore volume is less than the lower limit, sufficient occlusion ability and catalytic ability tend not to be exhibited.

  Next, the suitable method for manufacturing the organometallic complex of this invention is demonstrated. That is, first, a tetrakismonocarboxylic acid metal binuclear complex (the above general formula) is added to a solution in which a tetrapyridyl porphyrin and / or a tetrapyridyl porphyrin metal complex (the porphyrin derivative represented by the general formula (1)) is dissolved in a solvent. A solution in which the carboxylic acid metal complex represented by (2) is dissolved in an organic solvent for reaction is mixed and stirred for several days until crystals are sufficiently precipitated. Thereafter, the precipitated crystals are filtered, washed with the solvent used for the reaction, and vacuum-dried to obtain an organometallic complex suitable for the organometallic complex of the present invention (two-dimensional lattice represented by the general formula (3)) An organometallic complex having a structure as a repeating unit can be obtained.

  Such tetrapyridylporphyrin, tetrapyridylporphyrin metal complex, and tetrakismonocarboxylic acid metal binuclear complex are appropriately selected depending on the structure of the target organometallic complex of the present invention. The molar ratio of the addition amount of such tetrapyridylporphyrin and / or tetrapyridylporphyrin metal complex and the addition amount of the tetrakismonocarboxylic acid metal binuclear complex is 1: It is preferably about 0.1 to 1:20.

  The solvent for dissolving such tetrapyridylporphyrin or tetrapyridylporphyrin metal complex is not particularly limited, and examples thereof include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, and tetrachloroethane. Furthermore, the organic solvent for reaction is not particularly limited, and examples thereof include a solvent having a hydroxyl group. Examples of the organic solvent for reaction include methanol, ethanol, propanol, isopropanol, benzene, toluene, pentane, ethylbenzene, n-hexane, 3-methylpentane, n-heptane, cyclohexane, chloroform, ethylpropyl ether, allyl. Examples include ethyl ether, acetone, and ethyl methyl ketone.

  In addition, the method for mixing the solution is not particularly limited, and a known method can be appropriately selected and employed. For example, tetrapyridylporphyrin and / or tetrapyridylporphyrin metal complex is used in the lower layer of the tubule using a tubule. A liquid-liquid diffusion method in which a solution in which a tetrakismonocarboxylic acid metal binuclear complex is dissolved in an alcohol solvent is gently added after a solution in which is dissolved in a solvent can be employed.

  Moreover, as temperature conditions at the time of leaving for several days, about 0-200 degreeC is preferable, and it is more preferable that it is room temperature (25 degreeC)-about 80 degreeC. Moreover, as a pressure condition at the time of leaving for several days, it is preferable that it is about 0.01-10 MPa, and it is more preferable that it is about 0.1-1 MPa.

  Although the organometallic complex of the present invention has been described above, the storage material and catalyst of the present invention will be described below.

  The occlusion substance of the present invention contains the organometallic complex of the present invention. The catalyst of the present invention contains the organometallic complex of the present invention. Thus, since the occlusion substance or catalyst of the present invention each contains the organometallic complex of the present invention, both have an excellent occlusion ability and catalytic ability.

  Further, the occlusion material and catalyst of the present invention may be those containing the organometallic complex of the present invention, and the organometallic complex of the present invention itself constitutes the occlusion material or catalyst of the present invention, or The occlusion substance or catalyst of the present invention may be constituted by supporting the organometallic complex of the present invention on another substrate. Furthermore, the shape of the occlusion substance and catalyst of the present invention is not particularly limited, and examples thereof include powder, granules, membranes, spheres, and fibers. Further, it may be formed into a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, a corrugated plate shape, or the like.

  Such a storage material of the present invention is particularly useful as a hydrogen storage material, for example. In addition, the catalyst of the present invention is particularly useful as a catalyst for oxidation reaction, for example, and an alcohol compound important as an intermediate of organic synthesis reaction by performing selective oxidation reaction of saturated and unsaturated hydrocarbons. It can also be used as a catalyst for synthesizing oxygen-containing compounds such as epoxy compounds, or a catalyst for oxidizing low molecules such as hydrogen, nitrogen, carbon monoxide and sulfur-containing compounds. In addition, the catalyst of the present invention is used as an environmental purification catalyst for decomposing and removing various malodorous components, volatile organic compounds (VOC) or harmful components, for example, and deodorizing waste gas discharged in factories, vehicles, etc. It can be used for purification devices. Furthermore, the catalyst of the present invention is used not only in industrial fields such as chemical factories, food manufacturing factories, livestock farming, sewage / sewage treatment plants, but also in deodorizing / extinguishing, for example, in residences, offices, cars, common facilities, restaurants, etc. It can be used as a deodorant, deodorant / deodorant product, and deodorizer / deodorizer.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
<Manufacture of complex>
First, a solution in which 6 mg (0.0097 mmol) of tetrapyridylporphyrin was dissolved in 20 ml of chloroform was charged to the lower layer of the capillary tube, and 40 mg (0.1002 mmol) of copper (II) acetate monohydrate was dissolved in 20 ml of methanol. The solution was gently added from above and allowed to stand for several days under normal pressure (about 0.1 MPa) and room temperature (about 25 ° C.), and a single crystal was deposited by a liquid-liquid diffusion method.

Next, the obtained single crystal is filtered, washed with a mixed solvent of chloroform and methanol, and vacuum-dried, whereby M ¹ in the above general formula (1) is copper (II) (copper content). 100%), an organometallic complex of the present invention in which R ^{1 to} R ⁸ are each a hydrogen atom, R ⁹ in the general formula (2) is a methyl group, and M ² is copper (II) was obtained. .

<Single crystal X-ray structure analysis>
Single crystal X-ray structural analysis was performed on the obtained organometallic complex. In such single crystal X-ray structural analysis, the trade name “Saturn” manufactured by Rigaku Denshi Co., Ltd. was used as the X-ray structural analysis apparatus, and the product name “Crystal Structure” manufactured by Rigaku Denshi Co., Ltd. was used as the analysis software. . FIG. 1 is a diagram showing the direction of viewing the structure obtained by X-ray structural analysis, and FIG. 2 is a vector diagram showing the relationship between the (a), (b), and (c) directions shown in FIG. FIG. 3 shows a vector diagram showing the relationship between the directions (a), (d), and (e). Thus, the (a) direction indicates a direction perpendicular to the two-dimensional lattice plane, the (b) and (d) directions indicate directions parallel to the two-dimensional lattice plane, and the (c) direction indicates (a) and (b ) Direction and a direction at an angle of 45 °, respectively, and (e) direction indicates a direction at an angle of 45 ° with respect to each of the directions (a) and (d).

  FIG. 4 shows a two-dimensional lattice structure as viewed from the (a) direction obtained by such an X-ray structure analysis. FIG. 5 shows a state in which the two-dimensional lattice structure is viewed from the direction (a), and FIG. 6 shows a state in which the two-dimensional lattice structure is viewed from the direction (b). Further, FIG. 7 shows the state of the pores viewed from the respective directions (a), (b), (c), (d), and (e).

As apparent from FIGS. 4 to 7, in the obtained organometallic complex, M ¹ represented by the general formula (3) is copper (II) (copper content: 100%), and R ¹ to It was confirmed that each of the organometallic complexes has a two-dimensional lattice structure as a repeating unit in which R ⁸ is a hydrogen atom, R ⁹ is a methyl group, and M ² is copper (II). Further, as is clear from FIG. 7, it was confirmed that the obtained organometallic complex had pores in 9 directions. Moreover, the pore diameter of the largest pore among the plurality of pores having different diameters of such an organometallic complex is 1.0 nm, and it was confirmed that the organometallic complex has pores with a large diameter. .

<Measurement of specific surface area, pore volume, pore system distribution>
The adsorption / desorption isotherm of nitrogen gas at liquid nitrogen temperature was measured using a trade name “BELSORP 18” manufactured by Nippon Bell Co., Ltd. The measurement results are shown in FIG.

As a result of the measurement, the specific surface area was 812.08 m ² / g (calculated by the BET isotherm adsorption equation) and 1033.56 m ² / g (measurement range: 0 to 40 KPa, calculated by the Langmuir adsorption isotherm equation), and the pore volume was It was 0.4622 cm ³ .

<Measurement of hydrogen adsorption amount>
The hydrogen adsorption amounts at -199.3 ° C. and 23.3 ° C. were measured. A graph of the adsorption and desorption isotherm of hydrogen obtained from the measurement results is shown in FIG. As is clear from FIG. 9, it was confirmed that the organometallic complex of the present invention was excellent in the adsorption / desorption effect.

<Measurement of thermal stability>
Thermal stability and the generated gas were identified by TG-MS measurement. FIG. 10 is a graph showing the relationship between changes in the amount of various gases generated with respect to temperature.

  As is clear from FIG. 10, chloroform escapes from the pores at the first stage of weight loss (temperature range: 23 to 140 ° C.), and at the linker portion at the second stage of weight loss (temperature range: 190 to 400 ° C.). It was confirmed that decomposition of some copper (II) acetate occurred.

<Catalytic activity test>
The obtained organometallic complex was used as an oxidation catalyst for methyl mercaptan (CH ₃ SH). Dimethyl disulfide (CH ₃ —S—S—CH ₃ ) was selectively obtained as a product, and was found to function effectively as an oxidation catalyst.

(Example 2)
<Manufacture of complex>
First, instead of copper acetate (II) monohydrate, the same method as in Example 1 was adopted except that a copper (II) binuclear complex composed of two molecules of acetate ion and two molecules of benzoic acid was used. Single crystals were precipitated. FIG. 11 shows the structure of a copper (II) binuclear complex composed of two molecules of acetate ion and two molecules of benzoic acid used for the production of such an organometallic complex.

Then, after filtering the obtained single crystals were washed with chloroform, by performing vacuum drying, M ¹ in the general formula (1) is copper (II) (content of 100% copper), R ^{1 to} R ⁸ are each a hydrogen atom, and two of R ^{9 in} the general formula (2) are acetate ions, the remaining two of R ⁹ are benzoate ions, and M ² is copper. An organometallic complex of the present invention which is (II) was obtained.

<Single crystal X-ray structure analysis>
Single crystal X-ray structural analysis was performed on the obtained organometallic complex. In such single crystal X-ray structural analysis, the trade name “Rigaku CCD Mercury” manufactured by Rigaku Denshi Co., Ltd. is used as the X-ray structural analysis apparatus, and the product name “Crystal Structure” manufactured by Rigaku Denshi Co., Ltd. is used as the analysis software. Using. FIG. 12 shows a state in which the two-dimensional lattice structure viewed from the direction (c) is stacked.

As is clear from the results shown in FIG. 12, the organometallic complex obtained in Example 2 has M ¹ in the general formula (3) as copper (II) (copper content: 100%), R ^{1 to} R ⁸ are each a hydrogen atom, and two of R ^{9 in} the general formula (2) are acetate ions, the remaining two of R ⁹ are benzoate ions, and M ² is copper ( It was confirmed that the organometallic complex has a two-dimensional lattice structure (II) as a repeating unit. Further, as is clear from the results shown in FIG. 12, the organometallic complex obtained in Example 2 has a pore size of 1.0 nm or more and is an organometallic complex having large pores. confirmed.

  As described above, according to the present invention, there are provided an organometallic complex having a porphyrin structure capable of exhibiting advanced occlusion characteristics and excellent catalytic action, and an occlusion substance and a catalyst using the same. It becomes possible.

  Therefore, since the organometallic complex of the present invention is excellent in storage ability and catalytic ability, it is very useful as a hydrogen storage material, a material for an oxidation reaction catalyst, or the like.

It is a figure which shows the direction which sees the mode of the structure of the organometallic complex obtained in Example 1 by X-ray structural analysis. It is a vector diagram showing the relationship of the (a), (b), (c) direction shown in FIG. It is a vector diagram showing the relationship of the (a), (d), (e) direction shown in FIG. (A) It is a figure which shows the mode of the two-dimensional lattice structure of the organometallic complex obtained in Example 1 seen from the direction. (A) It is a figure which shows a mode that the two-dimensional lattice structure of the organometallic complex obtained in Example 1 seen from the direction was laminated | stacked. (B) It is a figure which shows a mode that the two-dimensional lattice structure of the organometallic complex obtained in Example 1 seen from the direction was laminated | stacked. It is a figure which shows the mode of the pore of the organometallic complex obtained in Example 1 seen from each direction of (a), (b), (c), (d), (e). 2 is a graph showing an adsorption / desorption isotherm of nitrogen gas at a liquid nitrogen temperature of the organometallic complex obtained in Example 1. FIG. 2 is a graph showing hydrogen adsorption and desorption isotherms at −199.3 ° C. and 23.3 ° C. of the organometallic complex obtained in Example 1. FIG. 2 is a graph showing the relationship of changes in the amount of various gases generated with respect to the temperature of the organometallic complex obtained in Example 1. 4 is a diagram showing the structure of a copper (II) binuclear complex composed of two molecules of acetate ion and two molecules of benzoic acid used in Example 2. FIG. (C) It is a figure which shows a mode that the two-dimensional lattice structure of the organometallic complex obtained in Example 2 seen from the direction was laminated | stacked.

Claims (6)

The following general formula (1):
Wherein (1), M ¹ is either indicates a metal atom coordinated to a nitrogen atom, or indicate two hydrogen atoms attached to the nitrogen atom, R ¹ to R ⁸ Waso respectively Indicates a hydrogen atom . ]
A porphyrin derivative represented by the following general formula (2):
[In Formula (2), R ⁹ may be the same or different, each represents a monovalent organic substituent selected from the group consisting of an alkyl group and an aryl group , and M ² may be the same or different. , Each represents a metal atom. ]
Is coupled in via the carboxylic acid metal complex represented,
The following general formula (3):
Wherein (3), ^{M 1} may be the same or different, have the same meanings as ^{M 1} in the general formula ^{(1), R 1} of R 1 to R ⁸ are in the general formula (1) to R ⁸ in the above formula, X is illustrates a carboxylic acid metal complex represented by the general formula (2). ]
Having a two-dimensional lattice structure represented by
An organometallic complex characterized by M ¹ in the general formula (1) is a metal atom selected from the group consisting of copper, ruthenium, rhodium, molybdenum, zinc, titanium, vanadium, aluminum, magnesium, cerium, tungsten, rhenium, and iron, or two 2. The organometallic complex according to claim 1, which is a hydrogen atom. M ² in the general formula (2) is a metal atom that can form a binuclear structure selected from the group consisting of copper, ruthenium, rhodium, molybdenum, chromium, zinc, tungsten, rhenium, technetium, and iron, respectively. The organometallic complex according to claim 1 or 2 , wherein Any of the claims 1 to 3, the pore diameter of the largest pore of the plurality of pores of different diameters repeating units of the 2-dimensional grating structure has is characterized in that a 0.6~2.5nm The organometallic complex according to claim 1. An occlusion substance comprising the organometallic complex according to any one of claims 1 to 4 . A catalyst comprising the organometallic complex according to any one of claims 1 to 4 .