TW202306958A - Metal organic structure, gas-storing agent comprising same, and gas storage method using same - Google Patents

Abstract

The present invention addresses the problem of providing: a novel metal organic structure having gas storage capability; and a gas-storing agent and a gas storage method, in each of which the metal organic structure is used. Provided is a metal organic structure in which a carboxylic acid ion represented by formula (1) is bound to a polyvalent metal ion (provided that a metal organic structure in which a carboxylic acid ion represented by formula (1) is bound to a bivalent copper ion in which X in formula (1) represents a sulfur atom, each of m1, m2, n1 and n2 represents 0, and both COO-'s are respectively bound to position-2 and position-8 is excluded). (In formula (1), X represents a sulfur atom or an oxygen atom; R1represents a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group; n1 and n2 independently represent any one integer of 0 to 3; when there are two or more R1's, the R1's may be the same as or different from each other; m1 and m2 independently represent 0 or 1; and when there are two or more L's, the L's may be the same as or different from each other.).

Description

Metal-organic structure, gas storage agent containing same, and gas storage method using same

The present invention relates to a metal-organic structure formed by bonding carboxylate ions and polyvalent metal ions, a gas storage agent comprising the metal-organic structure, and a gas storage comprising a step of bringing gas into contact with the metal-organic structure method. This application claims priority to Japanese Patent Application No. 2021-091175 filed on May 31, 2021, the contents of which are incorporated herein by reference.

Metal-organic structure (hereinafter, sometimes referred to as "MOF") is a solid having a polymer structure with spaces (i.e., pores) inside by combining metal ions and crosslinkable organic ligands that link them. As a porous material with functions such as gas storage and separation, it has received more attention in the past ten years. For example, it is known that a MOF with a surface area of 4000 m ² /g obtained by heating zirconium chloride and terphenyl dicarboxylic acid in dimethylformamide can store hydrogen, methane, acetylene and other gases (refer to patent Literature 1). Also, it is known that by mixing dicarboxylic acid represented by the following formula and Fe ₂ CoO(CH ₃ COO) ₆ or Fe ₃ O(CH ₃ COO) ₆ in N-methylpyrrolidone in the presence of acetic acid, Heated at 150° C. for 24 hours to obtain MOF in the form of dark brown crystals, which can store gases such as hydrogen, methane, carbon dioxide, and nitrogen (see Patent Document 2).

[chemical 1]

Also, Patent Document 2 discloses a metal-organic structure in which a dicarboxylic acid ion obtained from a dicarboxylic acid represented by the following formula is bonded to Fe.

[Chem 2]

In this development process, it is known that the structure of metal-organic structures varies greatly depending on the type of metal used, ligands, and reaction conditions, and it is required to develop a novel metal-organic structure with a gas storage function. prior art literature patent documents

Patent Document 1: International Publication No. 2009-133366 Patent Document 2: International Publication No. 2015-079229

[Problem to be solved by the invention]

The object of the present invention is to provide a novel metal-organic structure having a gas storage function, a gas storage agent and a gas storage method using the same. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research to solve the above-mentioned problems, and as a result, found a novel metal-organic structure obtained by using a specific dicarboxylic acid having a dibenzothiophene skeleton or a dibenzofuran skeleton as an organic ligand. Also, it was found that these novel metal-organic structures have a high hydrogen storage capacity, and thus completed the present invention.

(1) (式(1)中， X為硫原子或氧原子。 R ¹為羥基、C1～6烷基、C1～6烷氧基或鹵素基。 n1及n2為0～3之任一整數。R ¹為2以上時，各R ¹彼此可相同亦可不同。 L為以下式(2)所表示之2價基。 m1及m2為0或1。L為2以上時，各L彼此可相同亦可不同。 [化4]

或

式(2)中， R ²為羥基、C1～6烷基、C1～6烷氧基或鹵素基。 n3為0～4之任一整數。R ²為2以上時，各R ²彼此可相同亦可不同。 ＊及＊＊表示鍵結位置，＊＊表示與羧酸離子之鍵結位置)。 (2)如上述(1)之金屬有機構造體，其中多價金屬離子為選自由元素週期表之第2族～第13族之金屬所組成之群中之至少一種金屬離子。 (3)如上述(1)或(2)之金屬有機構造體，其進而包含輔助配位基作為構成成分。 (4)一種氣體儲藏劑，其包含如上述(1)至(3)中任一項之金屬有機構造體。 (5)一種氣體儲藏方法，其包括使氣體接觸如上述(1)至(3)中任一項之金屬有機構造體之步驟。 [發明之效果] That is, the present invention is specified by the matters shown below. (1) A metal-organic structure formed by bonding carboxylate ions represented by formula (1) with polyvalent metal ions (wherein, carboxylate ions represented by formula (1) and divalent metal ions are not included. It is formed by bonding copper ions, and X in formula (1) is a sulfur atom, m1, m2, n1 and n2 are all 0, COO ^- both are bonded to the metal organic structure of the 2-position and the 8-position) . [Chem 3]

(1) (In the formula (1), X is a sulfur atom or an oxygen atom. ^R1 is a hydroxyl group, a C1-6 alkyl group, a C1-6 alkoxy group or a halogen group. n1 and n2 are any integer from 0 to 3 When ^R is 2 or more, each ^R can be the same or different from each other. L is a divalent group represented by the following formula (2). m1 and m2 are 0 or 1. When L is 2 or more, each L can be mutually The same can also be different. [Chemical 4]

or

In formula (2), R ² is hydroxyl, C1-6 alkyl, C1-6 alkoxy or halogen. n3 is any integer of 0-4. When R ² is 2 or more, each R ² may be the same or different from each other. * and ** represent the bonding position, ** represent the bonding position with carboxylate ion). (2) The metal-organic structure according to (1) above, wherein the polyvalent metal ion is at least one metal ion selected from the group consisting of metals of Groups 2 to 13 of the Periodic Table of Elements. (3) The metal organic structure according to (1) or (2) above, further comprising an auxiliary ligand as a constituent. (4) A gas storage agent comprising the metal organic structure according to any one of (1) to (3) above. (5) A gas storage method comprising the step of bringing a gas into contact with the metal-organic structure according to any one of (1) to (3) above. [Effect of Invention]

The metal-organic structure of the present invention is relatively novel and can store gases such as hydrogen, carbon dioxide, and nitrogen.

The metal-organic structure system of the present invention is formed by bonding carboxylate ions represented by formula (1) and polyvalent metal ions (wherein, carboxylate ions represented by formula (1) and divalent copper ions are not included Bonded, and X in formula (1) is a sulfur atom, m1, m2, n1 and n2 are all 0, COO ^- both are bonded to the metal-organic structure at the 2-position and the 8-position).

[chemical 5]

In formula (1), X is a sulfur atom or an oxygen atom. R ¹ is hydroxyl, C1-6 alkyl, C1-6 alkoxy or halogen. n1 and n2 represent the number of R ¹ and are any integer of 0-3. When R ¹ is 2 or more, each R ¹ may be the same or different from each other. L is a divalent group represented by the following formula (2). m1 and m2 represent the number of L, which is 0 or 1. When L is 2 or more, each L may be the same or different from each other.

或

[chemical 6]

or

Regarding the C1-6 alkyl group as ^R1 , it may be a straight chain or a branched chain, for example: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl , isobutyl, second butyl, third butyl, isopentyl, neopentyl, 2-methyl-n-butyl, isohexyl, etc. Regarding the C1-6 alkoxy group as ^R1 , it can be exemplified: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, tertiary butoxyl, etc. The halogen group as R ¹ may, for example, be fluoro, chloro, bromo or iodo.

In formula (2), R ² is hydroxyl, C1-6 alkyl, C1-6 alkoxy or halogen. n3 represents the number of R ² and is any integer from 0 to 4. When R ² is 2 or more, each R ² may be the same or different from each other. Regarding the C1-6 alkyl group as ^R2 , it may be a straight chain or a branched chain, for example: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl , isobutyl, second butyl, third butyl, isopentyl, neopentyl, 2-methyl-n-butyl, isohexyl, etc. Regarding the C1-6 alkoxy group as R ² , for example: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, tertiary butoxyl, etc. The halogen group as R ² may, for example, be fluoro, chloro, bromo or iodo. * and ** indicate the binding position, ** indicates the binding position with the carboxylate ion. Terms such as "C1-6" indicate that the number of carbon atoms serving as the base of the mother nucleus is 1-6. As a carboxylate ion represented by formula (1), specifically, the compound etc. which are represented by the following formula can be illustrated. In the following formulae, the case where X is S is exemplified, but when X is O, the same structure can also be exemplified.

[chemical 7]

The polyvalent metal ion in the metal organic structure of the present invention is not particularly limited as long as it is a metal ion having a valence of two or more, and is preferably a metal ion selected from Groups 2 to 13 of the Periodic Table of Elements. At least one metal ion in the group consisting of, more preferably at least one metal ion selected from Zn, Al, Cu, Zr, Ni, Co, Cr, Fe, Sc, Mo, Mn, Ti and Mg. In the metal-organic structure of the present invention, the polyvalent metal ion bonded to the carboxylic acid ion represented by formula (1) may be one type, or two or more types.

These polyvalent metal ions are supplied in the form of various salts. As the metal salt, specifically, zinc nitrate (Zn(NO ₃ ) ₂ ･xH ₂ O), titanium nitrate (Ti(NO ₃ ) ₄ ･xH ₂ O), cobalt nitrate (Co(NO ₃ ) ₂ ･xH ₂ O), iron (III) nitrate (Fe(NO ₃ ) ₃ ･xH ₂ O), iron (II) nitrate (Fe(NO ₃ ) ₂ ･xH ₂ O), nickel (II) nitrate (Ni (NO ₃ ) ₂ ･xH ₂ O), copper (II) nitrate (Cu(NO ₃ ) ₂ ･xH ₂ O), aluminum (III) nitrate (Al(CH ₃ COO) ₃ ･xH ₂ O), magnesium nitrate (II)(Mg(NO ₃ ) ₂ ･xH ₂ O); zinc chloride (ZnCl ₂ ･xH ₂ O), titanium chloride (TiCl ₄ ･xH ₂ O), zirconium chloride (ZrCl ₄ ･xH ₂ O ), cobalt chloride (CoCl ₂ ･xH ₂ O), iron (III) chloride (FeCl ₃ ･xH ₂ O), iron (II) chloride (FeCl ₂ ･xH ₂ O), chromium (III) chloride (CrCl ₃ ･xH ₂ O), scandium (III) chloride (ScCl ₃ ･xH ₂ O), manganese (II) chloride (MnCl ₂ ･xH ₂ O); zinc acetate (Zn(CH ₃ COO) ₂ ･ xH ₂ O), titanium acetate (Ti(CH ₃ COO) ₄ ･xH ₂ O), zirconium acetate (Zr(CH ₃ COO) ₄ ･xH ₂ O), cobalt acetate (Co(CH ₃ COO) ₂ ･xH ₂ O), iron (III) acetate (Fe(CH ₃ COO) ₃ ･xH ₂ O), iron (II) acetate (Fe(CH ₃ COO) ₂ ･xH ₂ O); zinc sulfate (ZnSO ₄ ･xH ₂ O ), titanium sulfate (Ti(SO ₄ ) ₂ ･xH ₂ O), zirconium sulfate (Zr(SO ₄ ) ₂ ･xH ₂ O), cobalt sulfate (CoSO ₄ ･xH ₂ O), iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ ･xH ₂ O), iron (II) sulfate (FeSO ₄ ･xH ₂ O), magnesium (II) sulfate (MgSO ₄ ･xH ₂ O); zinc hydroxide (Zn(OH) ₂ ･ xH ₂ O), titanium hydroxide (Ti(OH) ₄ ･xH ₂ O), zirconium hydroxide (Zr(OH) ₄ ･xH ₂ O), cobalt hydroxide (Co(OH) ₂ ･xH ₂ O), Iron (III) hydroxide (Fe(OH) ₃ ･xH ₂ O), iron (II) hydroxide (Fe(OH) ₂ ･xH ₂ O); zinc bromide (ZnBr ₂ ･xH ₂ O), bromide Titanium (TiBr ₄ ･x H ₂ O), zirconium bromide (ZrBr ₄ ･xH ₂ O), cobalt bromide (CoBr ₂ ･xH ₂ O), iron(III) bromide (FeBr ₃ ･xH ₂ O), iron(II) bromide (FeBr ₂ ･xH ₂ O); Zinc Carbonate (ZnCO ₃ ･xH ₂ O), Cobalt Carbonate (CoCO ₃ ･xH ₂ O), Iron (III) Carbonate (Fe ₂ (CO ₃ ) ₃ ･xH ₂ O); Zirconium oxychloride (ZrOCl ₂ ･xH ₂ O), molybdenum (II) acetate dimer ((Mo(CH ₃ COO) ₂ ) ₂ ), etc. In addition, x is a number of 0-12. These can be used individually by 1 type or in mixture of 2 or more types.

The metal-organic structure of the present invention may contain an organic ligand other than the carboxylate ion represented by formula (1) as an auxiliary ligand. By making the metal organic structure contain auxiliary ligands, it is possible to introduce a higher order structure into the metal organic structure. Examples of such auxiliary ligands include terephthalic acid, phthalic acid, isophthalic acid, 5-cyanoisophthalic acid, 1,3,5-benzenetricarboxylic acid, 1,3, 5-tris(4-carboxyphenyl)benzene, 4,4'-dicarboxybiphenyl, 3,5-dicarboxypyridine, 2,3-dicarboxypyridine, 1,3,5-tris(4-carboxy phenyl)benzene, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 9,10-anthracene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, [1,1':4',1" ]Terphenyl-3,3",5,5"-tetracarboxylic acid, biphenyl-3,3",5,5"-tetracarboxylic acid, 3,3',5,5'-tetracarboxylic acid Diphenylmethane, 1,3,5-tris(4'-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)trimethanone, 1,2-bis(4-carboxy-3-nitrophenyl)ethylene, 1,2-bis(4-carboxy-3-aminophenyl)ethylene, trans,trans-muconic acid, fumar Acid, benzimidazole, imidazole, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyridoxine, 4,4'-bipyridine, 1,2-bis(4-pyridyl)ethylene , 1,2-bis(4-pyridyl)ethane, 2,7-diazapyrene, 4,4'-azobispyridine, 1,5-didine, phenanthrene, 2 bis(3-( 4-pyridyl)-2,4-pentanedionate) copper, etc. When using the carboxylate ion represented by the formula (1) and the auxiliary ligand, the mixing molar ratio is not particularly limited.

The method for producing the metal-organic structure of the present invention is not particularly limited, and any of the following methods can be used: solution methods such as solvent diffusion method, solvent stirring method, and hydrothermal method; microwaves are irradiated to the reaction solution to transform the entire system in a short time. The microwave method of uniform heating; the ultrasonic method, which is to repeatedly change the pressure in the reaction vessel by irradiating ultrasonic waves to the reaction vessel, and through the pressure change, the solvent forms bubbles and disintegrates, which is called cavitation The phenomenon of interaction, at this time, the high-energy field of about 5000 K and 10000 bar becomes the reaction field of each generation of locally formed crystals; the solid phase in which the metal ion generation source is mixed with the organic ligand without using a solvent Synthesis method; and LAG (liquid assisted grinding) method in which metal ion generating source and organic ligand are mixed by adding water of crystal water level, etc.

For example, the following steps are included: respectively preparing a first solution containing a metal compound and a solvent as a metal ion generation source, a second solution containing a carboxylate ion represented by formula (1) or a carboxylic acid as a precursor thereof and a solvent, and a step of a third solution containing an auxiliary ligand and a solvent as needed; and mixing the first solution, the second solution, and the third solution to prepare a reaction solution, and heating the reaction solution, thereby obtaining a metal organic structure body steps. The first to third solutions do not need to be prepared separately, for example, the above-mentioned metal compound, the carboxylate ion represented by formula (1) or the carboxylic acid as its precursor, the compound that becomes the auxiliary ligand, and the solvent can be mixed at one time to prepare a solution.

The mixing molar ratio of the above-mentioned metal compound and the carboxylate ion represented by the formula (1) or the carboxylic acid as its precursor can be arbitrarily selected according to the pore size and surface characteristics of the obtained metal-organic structure. The carboxylate ion represented by the formula (1) in 1 mole or the carboxylic acid as its precursor is preferably a metal compound of more than 1 mole, more preferably more than 1.1 mole, and more preferably More than 1.2 mol is used, more preferably 1.5 mol or more, still more preferably 2 mol or more, and still more preferably 3 mol or more.

The concentration of the aforementioned metal ions in the reaction solution is preferably in the range of 25-200 mmol/L. The concentration of the carboxylate ion represented by the formula (1) or the carboxylic acid as its precursor in the reaction liquid is preferably in the range of 10-100 mmol/L. The auxiliary coordination is preferably 10-100 mmol/L based on the concentration in the reaction solution.

The solvent used is not particularly limited, and can be selected from N,N-dimethylformamide (hereinafter, sometimes referred to as "DMF"), N,N-diethylformamide (hereinafter, sometimes Described as "DEF"), N,N-Dimethylacetamide (hereinafter sometimes described as "DMA"), N-methyl-2-pyrrolidone (hereinafter sometimes described as "NMP") , dimethylsulfone (hereinafter sometimes referred to as "DMSO"), and water may be used alone or in combination of two or more. Moreover, alcohols, such as methanol and ethanol, can also be mixed with these solvents, and can also be used.

The heating temperature of the reaction liquid is not particularly limited, and examples thereof include a range from room temperature to 140°C, a range from 70 to 140°C, and a range from 80 to 120°C.

The gas storage agent of the present invention includes the metal-organic structure of the present invention. The gas storage agent of the present invention may consist only of the metal-organic structure of the present invention, and may contain other components within a range that does not hinder its use as a gas storage agent. The shape of the gas storage agent of the present invention is not particularly limited, and examples thereof include powder, granule, and pellet. The metal-organic structure of the present invention can store hydrogen, methane, acetylene, carbon dioxide, nitrogen, and other gases by adsorbing or occluding them. The gas storage method using the metal-organic structure of the present invention is not particularly limited, but a method of contacting the metal-organic structure of the present invention with gas is preferred, and the contact method is not particularly limited. For example, a method of filling a tank with the metal-organic structure of the present invention as a gas storage tank and flowing gas into the tank, and carrying the metal-organic structure of the present invention on the inner wall of the tank A method of using the surface as a gas storage tank and letting gas flow into the groove, a method of forming a groove from a material including the metal-organic structure of the present invention as a gas storage tank, and letting gas flow into the groove, etc. [Example]

Hereinafter, examples of the present invention are given to illustrate the present invention in detail, but the technical scope of the present invention is not limited to these examples. As the precursor of the carboxylate ion represented by the formula (1) constituting the metal-organic structure of the present invention, organic ligands 1 to 9 shown in Table 1 below were used.

[Table 1]

In the case of including an auxiliary ligand, auxiliary ligands 1 to 10 shown in Table 2 were used as the auxiliary ligand.

[Table 2]

[Production Example 1] Synthesis of Organic Ligand 1 Dibenzothiophene (5.43 mmol) was dissolved in 20 mL of acetic acid and a solution of bromine (11.0 mmol) in acetic acid (5 mL) was added dropwise over 30 minutes. The reaction solution was stirred at room temperature for 2 hours, and further at 130° C. for 5 hours. The reaction solution was returned to room temperature, and the precipitated solid was filtered. The obtained solid was washed with water and recrystallized with acetic anhydride to obtain a colorless solid. The obtained solid was washed with water to obtain 2.00 mmol of 2,8-dibromodibenzothiophene as a colorless solid. The obtained 2,8-dibromodibenzothiophene (10.0 mmol) was dissolved in 100 mL of tetrahydrofuran, and cooled to -78°C. To the low-temperature reaction solution, 19.1 mmol of a hexane solution of n-butyllithium (1.57 M) was added dropwise over 30 minutes, followed by stirring at low temperature for 2 hours. After stirring, finely crushed dry ice was added and stirred for 1 hour. Furthermore, after stirring at room temperature for 1 hour, tetrahydrofuran was distilled off, and concentrated hydrochloric acid was added. The precipitated solid was filtered, washed with water and methanol, and dried at 100°C to obtain 8.12 mmol of 2,8-dicarboxydibenzothiophene (organic ligand 1) as a colorless solid. .

[Production Example 2] Synthesis of Organic Ligand 2 Except for using dibenzofuran instead of dibenzothiophene in Production Example 1, the same operation as Production Example 1 was carried out to obtain Organic Ligand 2 as a colorless solid.

[Production Example 3] Synthesis of Organic Ligand 3 2,8-dibromodibenzothiophene (3.31 mmol), potassium carbonate (16.5 mmol), 4-methoxycarbonylphenylboronic acid (8.26 mmol), tetrakis(triphenylphosphine) palladium (0.165 mmol), 20 mL of 1,2-diethoxyethane and 6 mL of water were stirred at 100°C for 2 days. After returning to room temperature, water was added, and the organic layer extracted with chloroform was dried over magnesium sulfate and filtered, and the filtrate was distilled under reduced pressure. After separation and purification by silica gel column chromatography, 0.877 mmol of 2,8-bis(4-methoxycarbonylphenyl)dibenzothiophene was obtained as a white solid. To the obtained 2,8-bis(4-methoxycarbonylphenyl)dibenzothiophene (0.877 mmol) were added potassium hydroxide (4.39 mmol), 20 mL of methanol, 20 mL of water, 20 mL of tetrahydrofuran, and Stir overnight at 90°C. Return to room temperature, add dilute hydrochloric acid, filter the precipitated solid, wash thoroughly with water, and dry it to obtain 0.877 mmol of 2,8-bis(4-carboxyphenyl)diphenyl in the form of a colorless solid And thiophene (organic ligand 3).

[Production Example 4] Synthesis of Organic Ligand 4 2,8-Dibromodibenzothiophene (3.31 mmol), copper(I) iodide (0.331 mmol), triphenylphosphine (0.661 mmol), bis(triphenylphosphine)palladium dichloride (0.661 mmol ), 4-methoxycarbonylphenylacetylene (9.92 mmol), and 30 mL of triethylamine were stirred at 120°C for 2 days. After returning to room temperature, water was added, the organic layer extracted with dichloromethane was dried over magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. After separation and purification by silica gel column chromatography, 2.30 mmol of 2,8-bis(4-methoxycarbonylphenylethynyl)dibenzothiophene was obtained as a white solid. Potassium hydroxide (10.0 mmol), 30 mL of methanol, 30 mL of water, and 30 mL of tetrahydrofuran were added to the obtained 2.00 mmol of 2,8-bis(4-methoxycarbonylphenylethynyl)dibenzothiophene, and stirred overnight at 90°C. Return to room temperature, add dilute hydrochloric acid, filter the precipitated solid, wash thoroughly with water, and dry it to obtain 1.50 mmol of 2,8-bis(4-carboxyphenylethynyl) in the form of a colorless solid Dibenzothiophene (organic ligand 4).

[Production Example 5] Synthesis of Organic Ligand 5 Except for using 2,8-dibromodibenzofuran instead of 2,8-dibromodibenzothiophene in Production Example 4, the same operation as Production Example 4 was carried out to obtain the organic ligand 5 as a colorless solid.

[Production Example 6] Synthesis of Organic Ligand 6 Dibenzothiophene (5.43 mmol) was dissolved in acetic acid (14 mL), and hydrogen peroxide solution (2.44 mL) was added dropwise. The reaction solution was stirred at 130°C for 4 hours. After returning to room temperature, the reaction solution was poured into water, and a colorless solid was precipitated. The obtained suspension was filtered, the colorless solid was fully washed with water and methanol, and dried to obtain 5.09 mmol of dibenzothiophene dioxide as a colorless solid. The obtained 4.62 mmol of dibenzothiophene dioxide and N-bromosuccinimide (9.24 mmol) were dissolved in sulfuric acid (150 mL), and stirred at room temperature for 24 hours. Slowly pour the obtained suspension into ice water, filter the obtained suspension, wash the colorless solid with water and methanol, and dry it to obtain 3.45 mmol of 3 ,7-Dibromodibenzothiophene dioxide. Lithium aluminum hydride (10.4 mmol) was added to the obtained 2.63 mmol of 3,7-dibromodibenzothiophene dioxide suspension in diethyl ether (40 mL), followed by heating and stirring at 50° C. for 1 hour. The obtained suspension was poured into ice water, and hydrochloric acid was added to make it acidic. The reaction solution was extracted with chloroform, the organic layer was dried over magnesium sulfate, and filtered, and the filtrate was distilled under reduced pressure. By recrystallizing the obtained crude product with acetone, 1.11 mmol of 3,7-dibromodibenzothiophene was obtained as a white solid. The obtained 5.17 mmol of 3,7-dibromodibenzothiophene was dissolved in 100 mL of tetrahydrofuran, and cooled to -78°C. 15.5 mmol n-butyllithium hexane solution (1.57 M) was added dropwise to the reaction solution at low temperature over 30 minutes, and stirred at low temperature for 2 hours. After stirring, finely crushed dry ice was added and stirred for 1 hour. Furthermore, after stirring at room temperature for 1 hour, tetrahydrofuran was distilled off, and concentrated hydrochloric acid was added. The precipitated solid was filtered, washed with water and methanol, and dried at 100°C to obtain 4.22 mmol of 3,7-dicarboxydibenzothiophene (organic ligand 6) as a colorless solid .

[Production Example 7] Synthesis of Organic Ligand 7 Except for using 3,7-dibromodibenzothiophene instead of 2,8-dibromodibenzothiophene in Production Example 3, the same operation as Production Example 3 was carried out to obtain the organic ligand 7 as a colorless solid.

[Production Example 8] Synthesis of Organic Ligand 8 Except for using 3,7-dibromodibenzothiophene instead of 2,8-dibromodibenzothiophene in Production Example 4, the same operation as Production Example 4 was carried out to obtain the organic ligand 8 as a colorless solid.

[Production Example 9] Synthesis of Organic Ligand 9 Dissolve dibenzothiophene (10.0 mmol) in hexane (10 mL), add N,N,N',N'-tetramethylethylenediamine (30.0 mmol), and cool to -78°C. A 30.0 mmol n-butyllithium hexane solution (1.57 M) was added dropwise to the reaction solution at low temperature over 30 minutes, and stirred at low temperature for 2 hours. After stirring, finely crushed dry ice was added and stirred for 1 hour. Furthermore, after stirring at room temperature for 1 hour, concentrated hydrochloric acid was added after distilling off hexane. The precipitated solid was filtered, washed with water and methanol, and dried at 100°C to obtain 4.44 mmol of 4,6-dicarboxydibenzothiophene (organic ligand 9) as a colorless solid. .

The 1H-NMR data of the obtained organic ligand are shown below. Organic Ligand 1 ¹ H-NMR (400 MHz, DMSO-d6) δ: 8.09 (2H, dd), 8.19 (2H, d), 8.95 (2H, d). Organic Ligand 2 ¹ H-NMR ( 400 MHz, DMSO-d6) δ: 7.84 (2H, d), 8.16 (2H, dd), 8.89 (2H, d). Organic Ligand 3 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.95 (2H, dd), 8.03-8.09 (8H, m), 8.17(2H, d), 9.02 (2H, d). Organic Ligand 4 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.70- 7.75 (6H, m), 8.00 (4H, d), 8.16(2H, d), 8.78 (2H, s). Organic Ligand 5 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.75 (4H , d), 7.78(2H, d), 7.83 (2H, d), 7.99(4H, d), 8.52 (2H, s). Organic Ligand 6 ¹ H-NMR (400 MHz, DMSO-d6) δ : 8.07 (2H, d), 8.55 (2H, dd), 8.68 (2H, s). Organic ligand 7 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.91 (2H, d), 7.95 ( 4H, d), 8.06(4H, d), 8.47(2H, s), 8.51 (2H, d). Organic ligand 8 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.69 (4H, d ), 7.72(2H, d), 7.98(4H, d), 8.36(2H, s), 8.47(2H, d). Organic Ligand 9 ¹ H-NMR (400 MHz, DMSO-d6) δ: 7.67 (2H, t), 8.20 (2H, dd), 8.70 (2H, dd).

[Example 1-1] Add 10 mL of DMF to organic ligand 1 (0.5 mmol) and zinc nitrate hexahydrate (1.0 mmol), and heat in an oven (reaction condition: 90° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 1-1 as a colorless solid.

[Example 1-2]～[Example 1-51] Except that the organic ligand, solvent, temperature, heating time, and the concentration of the organic ligand are reacted as shown in Table 3, the same operation as in Example 1-1 was carried out to obtain metal organic structure 1-2 ~1-51. The results are shown in Table 3. "Concentration (M)" in Table 3 was calculated as the ratio of organic ligands in the solvent. The solvent "DMF+MeOH" used in Examples 1-34 is a mixed solvent of 9 mL of DMF and 1 mL of MeOH. In the following tables, "concentration (M)" represents the concentration of the organic ligand calculated as the ratio of the organic ligand in the solvent.

[table 3] Example organic ligand solvent temperature(℃) Heating time (hr) Concentration (M) character 1-2 1 DMF 120 48 0.05 light brown solid 1-3 1 DEF 90 48 0.05 colorless solid 1-4 1 DEF 120 48 0.05 light brown solid 1-5 1 NMP 120 48 0.05 colorless solid 1-6 1 DMF 120 168 0.0217 colorless solid 1-7 1 DEF 120 48 0.0217 beige solid 1-8 1 DMF 120 48 0.025 colorless solid 1-9 2 DMF 90 48 0.05 colorless solid 1-10 2 DMF 120 48 0.05 Colorless solid + light brown solid 1-11 2 DEF 90 48 0.05 Colorless solid + light brown solid 1-12 2 DEF 120 48 0.05 Colorless solid + brown solid 1-13 3 DMF 90 48 0.05 light brown solid 1-14 3 DMF 120 48 0.05 brown solid 1-15 3 DEF 90 48 0.05 yellow solid 1-16 3 DEF 120 48 0.05 yellow solid 1-17 4 DMF 90 48 0.05 colorless solid 1-18 4 DMF 120 48 0.05 pale yellow solid 1-19 4 DEF 90 48 0.05 colorless solid 1-20 4 DEF 120 48 0.05 light brown solid 1-21 5 DMF 90 48 0.05 dark brown solid 1-22 5 DMF 120 48 0.05 black green solid 1-23 5 DEF 90 48 0.05 solid complexion 1-24 5 DEF 120 48 0.05 dark brown solid 1-25 5 NMP 120 168 0.05 dark brown solid 1-26 6 DMF 90 48 0.05 yellow solid 1-27 6 DMF 120 48 0.05 pale yellow solid 1-28 6 DEF 90 48 0.05 light brown solid 1-29 6 DEF 120 48 0.05 light brown solid 1-30 6 NMP 120 168 0.05 pale orange solid 1-31 6 DMF 120 48 0.0217 beige solid 1-32 6 DEF 120 48 0.0217 brown solid 1-33 6 DMF 90 336 0.0217 colorless solid 1-34 6 DMF+MeOH 120 168 0.0121 colorless solid 1-35 7 DMF 90 48 0.05 colorless solid 1-36 7 DMF 120 48 0.05 pale yellow solid 1-37 7 DEF 90 48 0.05 colorless solid 1-38 7 DEF 120 48 0.05 pale yellow solid 1-39 7 NMP 120 168 0.05 pale orange solid 1-40 7 DMSO 120 168 0.05 colorless solid 1-41 8 DMF 90 48 0.05 dark green solid 1-42 8 DMF 120 48 0.05 dark green solid 1-43 8 DEF 90 48 0.05 dark green solid 1-44 8 DEF 120 48 0.05 yellow ocher solid 1-45 9 DMF 90 48 0.05 pale yellow solid 1-46 9 DMF 120 48 0.05 colorless solid 1-47 9 DEF 90 48 0.05 pale yellow solid 1-48 9 DEF 120 48 0.05 light brown solid 1-49 9 DMF 120 48 0.0217 colorless solid 1-50 9 DEF 120 48 0.0217 beige solid 1-51 9 NMP 120 168 0.05 pale orange solid

[Example 2-1] Dissolve organic ligand 1 (0.5 mmol) in 7.5 mL of DMF, and add auxiliary ligand 1 (0.2 mmol) and zinc nitrate hexahydrate (0.5 mmol) to it, and place in an oven (reaction condition: 90°C , 48 hours) for heating. Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 2-1 as a colorless solid.

[Example 2-2]～[Example 2-33] Except that the organic ligand, auxiliary ligand, solvent, temperature, heating time, and the concentration of the organic ligand shown in Table 4 are reacted, the same operation as in Example 2-1 is carried out to obtain a metal organic Structures 2-2 to 2-33. The results are shown in Table 4. In Examples 2-5 and 2-7, a mixed solvent of 5 mL of DMF and 5 mL of NMP was used, and in Examples 2-6 and 2-8, a mixed solvent of 30 mL of DMF and 30 mL of NMP was used. solvent. Also, in Examples 2-23 and 2-24, a mixed solvent of 5 mL of DMF, 1 mL of water, and 2 mL of EtOH was used.

[Table 4] Example organic ligand auxiliary ligand solvent temperature(℃) Heating time (hr) Concentration (M) character 2-2 1 1 DEF 120 48 0.05 pale yellow solid 2-3 1 1 NMP 120 168 0.05 Orange solid + colorless solid 2-4 1 2 DMF 120 48 0.025 pale yellow solid 2-5 1 3 DMF+NMP 120 48 0.01 pale yellow solid 2-6 1 3 DMF+NMP 120 48 0.00167 light brown solid 2-7 1 4 DMF+NMP 120 48 0.01 light brown solid 2-8 1 4 DMF+NMP 120 48 0.00167 light brown solid 2-9 2 1 DMF 120 48 0.05 colorless solid 2-10 2 1 DEF 120 48 0.05 brown solid 2-11 3 1 DMF 120 48 0.05 Colorless solid + pink solid 2-12 3 1 DEF 120 48 0.05 Colorless solid + pink solid 2-13 4 1 DMF 120 48 0.05 pale yellow solid 2-14 4 1 DEF 120 48 0.05 light brown solid 2-15 5 1 DMF 120 48 0.05 gray solid 2-16 5 1 DEF 120 48 0.05 light brown solid 2-17 5 1 DMSO 120 168 0.05 black solid 2-18 6 1 DMF 120 48 0.05 pale yellow solid 2-19 6 1 DEF 120 48 0.05 pale yellow solid 2-20 6 2 DMA 120 48 0.01 colorless solid 2-21 6 2 DMF 120 48 0.01 beige solid 2-22 6 1 DMF 120 48 0.0667 pale orange solid 2-23 6 5 DMF4- _H2O ＋EtOH 80 48 0.0125 colorless solid 2-24 6 6 DMF + _H2O + EtOH 80 48 0.0125 colorless solid 2-25 6 2 DMF 80 48 0.02 pale yellow solid 2-26 7 1 DMF 120 48 0.05 colorless solid 2-27 7 1 DEF 120 48 0.05 colorless solid 2-28 7 1 DMSO 120 168 0.05 colorless solid 2-29 8 1 DMF 120 48 0.05 yellow ocher solid 2-30 8 1 DEF 120 48 0.05 yellow ocher solid 2-31 9 1 DMF 120 48 0.05 colorless solid 2-32 9 1 DEF 120 48 0.05 light brown solid 2-33 9 1 NMP 120 168 0.05 pale orange solid

[Example 3-1] Add 9.2 mL of DEF to organic ligand 1 (0.294 mmol) and aluminum nitrate nonahydrate (0.382 mmol), and heat in an oven (reaction condition: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 3-1 as a brown solid.

[Embodiment 3-2]～[Embodiment 3-8] Except that the organic ligand, solvent, temperature, heating time, and the concentration of the organic ligand are reacted as shown in Table 5, the same operation as in Example 3-1 was carried out to obtain the metal organic structure 3-2 ~3-8. The results are shown in Table 5.

[table 5] Example organic ligand solvent temperature(℃) Heating time (hr) Concentration (M) character 3-2 6 DMF 120 48 0.032 colorless solid 3-3 6 DEF 120 48 0.032 colorless solid 3-4 6 DMF 90 336 0.0217 colorless solid 3-5 6 DEF 90 48 0.0217 beige solid 3-6 9 DMF 120 48 0.032 yellow solid 3-7 9 DEF 120 48 0.032 brown solid 3-8 9 DMF 90 48 0.0217 pale orange solid

[Example 4-1] Add 9.2 mL of DEF to organic ligand 6 (0.2 mmol) and copper nitrate trihydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 4-1 as a light blue-green solid.

[Embodiment 4-2]～[Embodiment 4-8] Except for the organic ligand, solvent, temperature, and heating time shown in Table 6, the same operations as in Example 4-1 were performed to obtain metal organic structures 4-2 to 4-8. The results are shown in Table 6.

[Table 6] Example organic ligand solvent temperature(℃) Heating time (hr) character 4-2 6 DMF 90 48 light blue solid 4-3 6 DEF 90 48 light blue solid 4-4 6 DMA 90 48 light blue green solid 4-5 9 DMF 120 48 light blue green solid 4-6 9 DEF 120 48 light blue green solid 4-7 9 DMA 90 48 light blue green solid 4-8 9 DMA 120 48 light blue green solid

[Example 5-1] Dissolve organic ligand 1 (0.2 mmol) in 9.2 mL of DEF, and add auxiliary ligand 2 (0.2 mmol) and copper nitrate trihydrate (0.2 mmol) to it, and place in an oven (reaction condition: 120°C , 48 hours) for heating. Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 5-1 as a light blue-green solid.

[Example 5-2] ~ [Example 5-27] Except for the organic ligand, auxiliary ligand, solvent, and temperature shown in Table 7, the same operations as in Example 5-1 were performed to obtain metal organic structures 5-2 to 5-27. The results are shown in Table 7.

[Table 7] Example organic ligand auxiliary ligand solvent temperature(℃) character 5-2 1 5 DMF 120 dark blue green solid 5-3 1 7 DMF 120 light blue green solid 5-4 1 8 DMF 120 light blue green solid 5-5 1 9 DMF 120 light blue green solid 5-6 1 2 DMA 120 dark blue solid 5-7 1 7 DMA 120 blue-green solid 5-8 1 8 DMA 120 blue-green solid 5-9 1 9 DMA 120 dark blue green solid 5-10 1 5 DMF 90 dark blue solid 5-11 1 6 DMF 90 dark blue solid 5-12 1 6 DMF 120 dark blue solid 5-13 1 6 DMF 120 light black yellow solid 5-14 1 6 DEF 120 sky blue solid 5-15 1 6 DMA 120 white purple solid 5-16 1 6 NMP 120 white purple solid 5-17 6 2 DMA 120 light blue green solid 5-18 6 5 DMA 120 light blue green solid 5-19 6 7 DMA 120 light blue green solid 5-20 6 8 DMA 120 light blue green solid 5-21 6 9 DMA 120 light blue green solid 5-22 9 1 DMA 120 dark blue solid 5-23 9 2 DMA 120 green solid 5-24 9 5 DMA 120 green solid 5-25 9 7 DMA 120 green solid 5-26 9 8 DMA 120 green solid 5-27 9 9 DMA 120 green solid

[Example 6-1] Add 9.2 mL of DMF to Organic Ligand 1 (0.2 mmol) and zirconium chloride (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 6-1 as a brown solid.

[Embodiment 6-2]～[Embodiment 6-8] Except for performing the reaction with the organic ligand, solvent, and temperature shown in Table 8, the same operations as in Example 6-1 were performed to obtain metal organic structures 6-2 to 6-8. The results are shown in Table 8.

[Table 8] Example organic ligand solvent temperature(℃) character 6-2 1 DEF 120 Colorless solid + pale yellow solid 6-3 6 DMF 120 colorless solid 6-4 6 DEF 120 beige solid 6-5 6 DMF 90 colorless solid 6-6 6 DEF 90 colorless solid 6-7 9 DMF 120 colorless solid 6-8 9 DEF 120 colorless solid

[Example 7-1] Dissolve the organic ligand 6 (0.2 mmol) in 18 mL of DMF, add trifluoroacetic acid (1.7 mL) and zirconium chloride (0.2 mmol) as additives, and place in an oven (reaction conditions: 120°C, 48 hours) for heating. Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 7-1 as a light blue-green solid.

[Embodiment 7-2]～[Embodiment 7-11] Except for reacting with the additives, heating temperature, and concentration of the organic ligand shown in Table 9, the same operations as in Example 7-1 were carried out to obtain metal organic structures 7-2 to 7-11. The results are shown in Table 9.

[Table 9] Example Additives Heating time (hr) Concentration (M) character 7-2 Acetic acid 48 0.011 colorless solid 7-3 hydrochloric acid 48 0.0116 colorless solid 7-4 Acetic acid 168 0.0102 colorless solid 7-5 formic acid 168 0.0102 colorless solid 7-6 Trifluoroacetate 48 0.0116 colorless solid 7-7 formic acid 48 0.0116 colorless solid 7-8 hydrochloric acid 168 0.0111 colorless solid 7-9 nitric acid 168 0.0111 colorless solid 7-10 Acetic anhydride 168 0.0111 colorless solid 7-11 benzoic acid 168 0.0111 colorless solid

[Example 8-1] Add 9.2 mL of DMF to organic ligand 1 (0.2 mmol) and nickel nitrate hexahydrate (0.2 mmol), and heat in an oven (reaction condition: 120° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 8-1 as a brown solid.

[Embodiment 8-2]～[Embodiment 8-6] Except for the organic ligand, solvent, heating temperature, and organic ligand concentration shown in Table 10 below, the same operation as in Example 8-1 was performed to obtain metal organic structures 8-2 to 8. -6. The results are shown in Table 10.

[Table 10] Example organic ligand solvent Heating time (hr) Concentration (M) character 8-2 1 DMF 48 0.032 colorless solid 8-3 6 DEF 48 0.032 colorless solid 8-4 6 DMF 336 0.0217 colorless solid 8-5 9 DEF 48 0.0217 beige solid 8-6 9 DMF 48 0.032 yellow solid

[Example 9-1] Add 9.2 mL of DMF to organic ligand 1 (0.2 mmol) and cobalt nitrate hexahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 9-1 as a lavender solid.

[Example 9-2] ~ [Example 9-6] Except for carrying out the reaction with the organic ligand, solvent, heating time, and the concentration of the organic ligand shown in Table 11, the same operation as in Example 9-1 was carried out to obtain metal organic structures 9-2 to 9. -6. The results are shown in Table 11.

[Table 11] Example organic ligand solvent Heating time (hr) Concentration (M) character 9-2 1 DMF 48 0.0217 strong brown solid 9-3 6 DEF 48 0.0217 lavender solid 9-4 6 DMF 48 0.0217 light tea brown solid 9-5 9 DEF 48 0.0217 purple solid 9-6 9 DMF 48 0.0217 lavender solid

[Example 10-1] Add 9.2 mL of DMF to organic ligand 1 (0.2 mmol) and chromium chloride hexahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 10-1 as a dark green solid.

[Example 10-2] ~ [Example 10-10] Except for carrying out the reaction with the organic ligand, solvent, temperature, and heating time shown in Table 12, the same operations as in Example 10-1 were carried out to obtain metal organic structures 10-2 to 10-10. The results are shown in Table 12.

[Table 12] Example organic ligand solvent temperature(℃) Heating time (hr) character 10-2 1 DEF 120 48 dark green solid 10-3 6 DMF 120 48 light green solid 10-4 6 DEF 120 48 light green solid 10-5 6 DMF 90 48 light green solid 10-6 6 DEF 90 48 light blue solid 10-7 9 DMF 120 48 light green solid 10-8 9 DEF 120 48 Pale yellow-green solid 10-9 9 DMF 90 48 light green solid 10-10 9 DEF 90 48 light green solid

[Example 11-1] Add 9.2 mL of DMF to Organic Ligand 1 (0.2 mmol) and ferric chloride hexahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 11-1 as an orange solid.

[Example 11-2] ~ [Example 11-6] Except for carrying out the reaction with the organic ligand, solvent, and temperature shown in Table 13 below, the same operations as in Example 11-1 were carried out to obtain metal organic structures 11-2 to 11-6. The results are shown in Table 13.

[Table 13] Example organic ligand solvent temperature(℃) character 11-2 1 DEF 120 orange solid 11-3 1 DEF 90 dark red solid 11-4 6 DEF 120 orange solid 11-5 9 DMF 120 orange solid 11-6 9 DEF 120 orange solid

[Example 12-1] Add 9.2 mL of DMF to organic ligand 1 (0.2 mmol) and scandium chloride hexahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 12-1 as a colorless solid.

[Example 12-2] ~ [Example 12-6] Except for carrying out the reaction with the organic ligand, solvent, temperature, and heating time shown in Table 14, the same operations as in Example 12-1 were performed to obtain metal organic structures 12-2 to 12-6. The results are shown in Table 14.

[Table 14] Example organic ligand solvent temperature(℃) Heating time (hr) character 12-2 1 DEF 90 336 colorless solid 12-3 6 DMF 120 48 colorless solid 12-4 6 DEF 120 48 colorless solid 12-5 9 DMF 120 48 colorless solid 12-6 9 DEF 120 48 colorless solid

[Example 13-1] Add 9.2 mL of DEF to organic ligand 1 (0.2 mmol) and molybdenum acetate dimer (0.1 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 13-1 as a brown solid.

[Example 13-2] ~ [Example 13-3] Except for carrying out the reaction with the organic ligand, solvent, temperature, and heating time shown in Table 15, the same operations as in Example 13-1 were carried out to obtain metal-organic structures 13-2 to 13-3. The results are shown in Table 15.

[Table 15] Example organic ligand solvent temperature(℃) Heating time (hr) character 13-2 1 DMF 90 336 brown solid 13-3 9 DMF 120 168 colorless solid

[Example 14-1] Add 9.2 mL of DMF to Organic Ligand 1 (0.2 mmol) and manganese chloride tetrahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 14-1 as a colorless solid.

[Example 14-2] ~ [Example 14-7] Except for carrying out the reaction with the organic ligand, solvent, temperature, and heating time shown in Table 16, the same operations as in Example 14-1 were carried out to obtain metal organic structures 14-2 to 14-7. The results are shown in Table 16.

[Table 16] Example organic ligand solvent temperature(℃) Heating time (hr) character 14-2 1 DMF 90 336 colorless solid 14-3 6 DMF 120 168 pale yellow solid 14-4 6 DEF 120 168 pale yellow solid 14-5 9 DMF 120 168 beige solid 14-6 9 DEF 120 168 beige solid 14-7 9 DMF 90 336 pale orange solid

[Example 15-1] Mix organic ligand 6 (0.01 mmol) with 10 mL of MeOH, 2 mL of EtOH, 2 mL of water, and add auxiliary ligand 5 (0.02 mmol), potassium carbonate (0.02 mmol) and chloride Manganese tetrahydrate (0.02 mmol) was heated in an oven (reaction condition: 80° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 15-1 as a colorless solid.

[Example 16-1] Add 9.2 mL of DMF to organic ligand 6 (0.2 mmol) and magnesium nitrate hexahydrate (0.2 mmol), and heat in an oven (reaction conditions: 120° C., 168 hours). Return to room temperature and remove the supernatant. After washing with 10 mL of DMF, the solvent was removed and replaced with chloroform. Add 10 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 16-1 as a colorless solid.

[Example 16-2] ~ [Example 16-5] Except for carrying out the reaction with the organic ligand, solvent, temperature, and heating time shown in Table 17, the same operations as in Example 16-1 were carried out to obtain metal organic structures 16-2 to 16-5. The results are shown in Table 17.

[Table 17] Example organic ligand solvent temperature(℃) Heating time (hr) character 16-2 6 DEF 120 168 pale yellow solid 16-3 9 DMF 120 168 colorless solid 16-4 9 DEF 120 168 light brown solid 16-5 9 DEF 90 336 pale orange solid

[Example 17-1] Add 2 mL of DMF to organic ligand 6 (0.1 mmol) and zirconium oxychloride (0.1 mmol), and heat in an oven (reaction condition: 120°C, 48 hours). Return to room temperature and remove the supernatant. After washing with 5 mL of DMF, the solvent was removed and replaced with chloroform. Add 5 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was carried out at 150° C. for 5 hours to obtain metal organic structure 17-1 as a pale yellow solid.

[Example 18-1] Add 2 mL of DMF to organic ligand 6 (0.1 mmol) and titanium chloride (0.1 mmol), and heat in an oven (reaction condition: 120° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 5 mL of DMF, the solvent was removed and replaced with chloroform. Add 5 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 18-1 as a pale yellow solid.

[Example 19-1] Organic ligand 6 (0.1 mmol), ORGATIX TC-400 (Ti(OiC ₃ H ₇ ) ₂ (C ₆ H ₁₄ O ₃ N) ₂ ) manufactured by Matsumoto Fine Chemical Co., Ltd. (0.1 mmol) was added with 2 mL of DMF, and heated in an oven (reaction condition: 120°C, 48 hours). Return to room temperature and remove the supernatant. After washing with 5 mL of DMF, the solvent was removed and replaced with chloroform. Add 5 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 19-1 as a colorless solid.

[Example 20-1] The organic ligand 6 (0.1 mmol) was dissolved in 2 mL of DMF, and the auxiliary ligand 10 (0.1 mmol) and zinc nitrate hexahydrate (0.1 mmol) as a metal reagent were added thereto. Conditions: heating at 120° C., 48 hours). Return to room temperature and remove the supernatant. After washing with 5 mL of DMF, the solvent was removed and replaced with chloroform. Add 5 mL of chloroform and soak overnight. After removal of chloroform, vacuum drying was performed at 150° C. for 5 hours to obtain metal organic structure 20-1 as a colorless solid.

[Example 20-2] ~ [Example 20-13] Except for using the metal salt or metal compound reagent shown in Table 18 below, the same operation as in Example 20-1 was carried out to obtain metal organic structures 20-2 to 20-13. The results are shown in Table 18.

[Table 18] Example Metal salt or metal compound reagent character 20-2 Cobalt nitrate hexahydrate purple solid 20-3 copper nitrate trihydrate light blue solid 20-4 Iron nitrate nonahydrate brown solid 20-5 Aluminum nitrate nonahydrate colorless solid 20-6 Chromium nitrate nonahydrate dark green solid 20-7 Magnesium nitrate hexahydrate pale yellow solid 20-8 Nickel nitrate hexahydrate greenish white solid 20-9 Manganese chloride dihydrate pale yellow solid 20-10 Zirconium chloride colorless solid 20-11 Zirconium oxychloride colorless solid 20-12 Titanium chloride yellow solid 20-13 ORGATIX TC - 400 (Ti(OiC ₃ H ₇ ) ₂ (C ₆ H _{1 4} O ₃ N) ₂ ) colorless solid

(Measurement of BET specific surface area and hydrogen storage capacity) The BET (Brunauer-Emmett-Teller, Buert) specific surface area and hydrogen storage capacity at 77K-atmospheric pressure were measured for a part of the obtained metal-organic structure. The BET specific surface area and the hydrogen storage capacity at 77K-atmospheric pressure were measured using a gas adsorption capacity measuring device Tristar-II (manufactured by Micromeritics). The BET specific surface area was calculated by the following method. About 50 mg of the metal-organic structure was put into the glass tank. The inside of the glass cell was depressurized to vacuum at a temperature of 135° C., and dried for 6 hours. Install the glass tank on the gas adsorption capacity measuring device, and immerse it in a constant temperature bath filled with liquid nitrogen. Slowly increase the pressure of nitrogen contained in the glass tank. The measurement was performed until the pressure of nitrogen introduced into the glass tank reached 1.0×10 ⁵ Pa. The hydrogen storage capacity at 77K normal pressure was calculated by the following method. After nitrogen was measured, the gas type was changed to hydrogen for measurement. Slowly increase the pressure of the hydrogen contained in the glass tank. The measurement was performed until the pressure of hydrogen introduced into the glass cell reached 1.0×10 ⁵ Pa. Table 19 shows the results of the measured BET specific surface area. The measured hydrogen storage capacity at 77K-atmospheric pressure is shown in Table 19.

[Table 19] metal organic structure number BET specific surface area (m ² /g) Hydrogen storage capacity (wt%) 1-27 371 0.533 1-31 727 0.831 1-34 1034 0.920 1-40 25.1 0.676 2-5 1879 0.754 2-6 1218 0.558 3-2 889 1.064 3-3 1070 1.216 3-4 633 0.880 3-5 479 0.649 3-6 311 0.634 4-2 226 0.564 5-1 146 0.646 5-2 680 1.699 5-4 211 0.563 5-6 183 0.842 5-8 195 0.842 5-9 30.4 0.504 5-10 501 1.116 5-11 352 0.793 5-12 316 0.663 5-15 34.89 0.513 5-17 183 0.842 5-18 113 0.695 5-22 795 1.043 6-3 360 0.581 6-4 345 0.656 6-5 339 0.525 7-1 1968 1.767 7-2 1788 1.722 7-3 646 0.779 7-4 1742 1.660 7-5 1535 1.486 7-6 1404 1.386 7-7 1251 1.288 7-8 1353 1.337 7-9 1873 1.562 7-10 1596 1.536 7-11 1990 1.758 10-3 618 0.913 10-4 514 0.778 10-5 334 0.693 10-6 484 0.731 10-7 117 0.774 10-8 49 0.592 10-10 7.34 0.507 11-1 364 0.844 11-2 360 0.805 12-1 344 0.661 12-2 39.1 0.716 14-1 44.3 0.843 14-6 37.8 0.674 16-4 67.2 0.737 17-1 746.6 0.914 18-1 535.9 0.721 19-1 220.2 0.673 20-1 213.5 0.717 20-2 393.1 0.932 20-3 148.3 0.484 20-4 321.1 0.606 20-5 688.3 0.874 20-6 1.275 0.734 20-7 55.95 0.292 20-8 682.6 1.492 20-9 70.56 0.185 20-10 501.8 0.749 20-11 1080 1.190 20-12 482.3 0.784 20-13 129.7 0.479 [Industrial availability]

The metal-organic structure of the present invention can store gases such as hydrogen at a practical level. Therefore, it can be applied to the energy field using hydrogen, such as a fuel cell.

Claims (5)

A metal-organic structure, which is formed by bonding carboxylate ions represented by formula (1) and polyvalent metal ions (wherein, excluding carboxylate ions represented by formula (1) and divalent copper ions bonded, and X in the formula (1) is a sulfur atom, m1, m2, n1 and n2 are all 0, COO ^- both are bonded to the metal-organic structure at the 2-position and the 8-position), [Chem. 1]

(In formula (1), X is a sulfur atom or an oxygen atom, R ¹ is hydroxyl, C1-6 alkyl, C1-6 alkoxy or halogen, n1 and n2 are any integer from 0 to 3, R ¹ When it is 2 or more, each ^R1 may be the same or different from each other, L is a divalent group represented by the following formula (2), m1 and m2 are 0 or 1, and when L is 2 or more, each L may be the same or different from each other different; [chemical 2]

or

In formula (2), R ² is hydroxyl, C1-6 alkyl, C1-6 alkoxy or halogen group, n3 is any integer from 0 to 4, and when R ² is 2 or more, each R ² can be the same It can also be different, * and ** represent the bonding position, ** represents the bonding position with the carboxylate ion). The metal-organic structure according to claim 1, wherein the polyvalent metal ion is at least one metal ion selected from the group consisting of metals from Groups 2 to 13 of the Periodic Table of Elements. The metal organic structure according to claim 1 or 2, further comprising an auxiliary ligand as a constituent. A gas storage agent comprising the metal-organic structure according to any one of claims 1 to 3. A gas storage method comprising the step of bringing gas into contact with the metal-organic structure according to any one of claims 1 to 3.