METAL-ORGANIC FRAMEWORK HAVING TEREPHTHALIC ACID BASED LIGAND

Abstract

Despite the fact that the amount and type of gas to be stored may vary in accordance with the type of substituent, metal-organic frameworks only using a terephthalic acid having substituents within the limited range have been produced conventionally. An object of the present invention is to provide a novel metal-organic framework using a 2,5-disubstituted terephthalic acid. A metal-organic framework comprising a carboxylate ion of formula (I) and a multivalent metal ion bound to each other is a novel metal-organic framework, enabling a gas such as hydrogen and nitrogen to be store efficiently. (wherein in formula (I), X is an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclyl group or —Si(R.sup.1) (R.sup.2) (R.sup.3) ; and Y is a single bond, an alkylene group, —O—, —S—, —S(O)—, —SO.sub.2—, —N(R.sup.4)— or a group formed by a combination thereof; provided that X—Y— is a phenyl group, a benzyloxy group, a pyrazol-1-yl group or a group of formula (II) except for a case where m is 3, 6, 8, 9, 10, 11 and 12).

##STR00001##

Claims

1. A metal-organic framework comprising a carboxylate ion of formula (I) and a multivalent metal ion bound to each other: ##STR00014## wherein in formula (I), X is an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclyl group or —Si(R.sup.1)(R.sup.2)(R.sup.3); wherein R.sup.1 to R.sup.3 each independently is a hydrogen atom, an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group; Y is a single bond, an alkylene group, —O—, —S—, —S(O)—, —SO.sub.2—, —N(R.sup.4)— or a group formed by a combination thereof; and R.sup.4 is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted arylalkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heterocyclyl group; provided that X—Y— is a phenyl group, a benzyloxy group, a pyrazol-1-yl group or a group of formula (II) except fora case where m is 3, 6, 8, 9, 10, 11 and 12: ##STR00015##

2. The metal-organic framework according to claim 1, wherein the multivalent metal ion is an ion of at least one metal selected from the group consisting of Groups 2 to 13 metals in the periodic table of elements.

3. The metal-organic framework according to claim 1, wherein the multivalent metal ion is an ion of at least one metal selected from Zn, Fe, Co, Ni, Cu, Al, Zr and Mg.

4. The metal-organic framework according to claim 1, further comprising, as a constituent, an organic ligand other than an organic ligand of formula (I).

5. A method for storing a gas, comprising a step of contacting a gas with the metal-organic framework according to claim 1 to cause the gas to be adsorbed inside the metal-organic framework.

Description

EXAMPLES

[0157] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0158] The structures of carboxylic acids as the precursors of Organic ligands 1 to 31, of formula (I), used in the examples (hereinafter referred to as “Organic ligands” including the carboxylic acids as the precursors) are shown in Table 1.

[0159] Abbreviations in Table 1 denote the following meaning.

[0160] Me: methyl group, Ph: phenyl group, Py: pyridyl group, c-Pr: cyclopropyl group, c-Hex: cyclohexyl group, O: oxygen atom, N: nitrogen atom, S: sulfur atom, Cl: chlorine atom, F: fluorine atom, H: hydrogen atom, C: carbon atom.

[0161] The number in X—Y— in Table 1 represents the substitution position. For example, 2-MePh is a 2-methylphenyl group, in which, the position at which a phenyl group is bound to the benzene ring in formula (I) is taken as the position 1, and the position 2 is substituted with a methyl group.

TABLE-US-00001 TABLE 1 (I) [00013] Organic ligand number X—Y—  1 2-MePh  2 3-MePh  3 4-MePh  4 2,6-diMePh  5 2-ClPh  6 3-ClPh  7 2-CF.sub.3Ph  8 3-CF.sub.3Ph  9 4-CF.sub.3Ph 10 3-Py 11 4-PyO 12 c-Pr 13 c-Hex 14 PhO 15 3-MePhO 16 2-MePhO 17 4-MePhO 18 4-ClPhO 19 PhNH 20 Me.sub.3Si 21 2-naphtylO 22 4-MeOPhO 23 3-thienyl 24 4-ClPh 25 4-MeOPh 26 3-MeOPh 27 2-MeOPh 28 3-furyl 29 2-MeSPh 30 3-MeSPh 31 4-MeSPh

[Production Example 1] Synthesis of Organic Ligand 1

[0162] Diethyl 2,5-dibromoterephthalic acid (5.0 mmol), o-methylphenylboronic acid (12.5 mmol), tetrakis(triphenylphosphine)palladium (0.05 mmol), 10 mL of a 2 M sodium carbonate aqueous solution, 35 mL of toluene and 10 mL of ethanol were heated under nitrogen at 90° C. for 36 hours. It was returned to room temperature, water was added thereto, and the solution was partitioned. The organic layer was dried over magnesium sulfate and filtered. The filtrate was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (chloroform). 1.5 g (3.7 mmol) of diethyl 2,5-di(o-methylphenyl)terephthalate was obtained as a yellow solid. Potassium hydroxide (100 mmol), 50 mL of ethanol and 40 mL of water were added to the obtained yellow solid and heated at 100° C. for 2 hours. It was returned to room temperature, and concentrated hydrochloric acid was added thereto. It was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and then filtered. The filtrate was distilled off under reduced pressure to obtain 1.2 g (3.46 mmol) of Organic ligand 1.

[Production Example 2] Synthesis of Organic Ligand 2

[0163] Organic ligand 2 was obtained by the same operation as in Production Example 1 except that m-methylphenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 3] Synthesis of Organic Ligand 4

[0164] Diethyl 2,5-dibromoterephthalate (5.0 mmol), 2,6-dimethylphenylboronic acid (12.5 mmol), tris (dibenzylideneacetone)dipalladium (0.25 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (1.0 mmol), potassium phosphate (15 mmol) and 50 mL of toluene were refluxed under nitrogen for 2 days. It was returned to room temperature and filtered through Celite. The filtrate was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (chloroform). The solid was washed with hexane and dried to obtain 2.1 mmol of diethyl 2,5-bis(2,6-dimethylphenyl)terephthalate as a colorless solid. Potassium hydroxide (40 mmol), 50 mL of ethanol and 20 mL of water were added to the obtained solid and heated at 100° C. for 15 hours. It was returned to room temperature, and concentrated hydrochloric acid was added thereto. It was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and then filtered. The filtrate was distilled off under reduced pressure to obtain 0.8 g (2.1 mmol) of Organic ligand 4.

[Production Example 4] Synthesis of Organic Ligand 5

[0165] Organic ligand 5 was obtained by the same operation as in Production Example 1 except that o-chlorophenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 5] Synthesis of Organic Ligand 6

[0166] Organic ligand 6 was obtained by the same operation as in Production Example 1 except that m-chlorophenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 6] Synthesis of Organic Ligand 7

[0167] Diethyl 2,5-dibromoterephthalic acid (5.0 mmol), o-trifluoromethylphenylboronic acid (12.0 mmol), [1,1′-bis(diphenylphosphino) ferrocene]palladium(II) dichloride dichloromethane adduct (0.25 mmol), potassium phosphate (20 mmol) and 20 mL of dimethoxyethane were refluxed under nitrogen for 1 day. It was returned to room temperature, washed with water, extracted with ethyl acetate, and then the organic layer was dried over magnesium sulfate. After filtration, the filtrate was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (chloroform). The solid was washed with hexane and dried to obtain 2.2 mmol of diethyl 2,5-bis(o-trifluoromethylphenyl)terephthalate. Potassium hydroxide (40 mmol), 50 mL of ethanol and 20 mL of water were added to the obtained solid and heated at 100° C. for hours. It was returned to room temperature, and concentrated hydrochloric acid was added thereto. It was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and then filtered. The filtrate was distilled off under reduced pressure to obtain 0.8 g (1.9 mmol) of Organic ligand 7.

[Production Example 7] Synthesis of Organic Ligand 8

[0168] Organic ligand 8 was obtained by the same operation as in Production Example 6 except that m-trifluoromethylphenylboronic acid was used instead of o-trifluoromethylphenylboronic acid.

[Production Example 8] Synthesis of Organic Ligand 9

[0169] Organic ligand 9 was obtained by the same operation as in Production Example 6 except that p-trifluoromethylphenylboronic acid was used instead of o-trifluoromethylphenylboronic acid.

[Production Example 9] Synthesis of Organic Ligand 10

[0170] 2,5-Dibromo-p-xylene (5.0 mmol), 3-pyridylboronic acid (12.0 mmol), tetrakis(triphenylphosphine)palladium (0.5 mmol), sodium hydroxide (20 mmol), 20 mL of toluene, 15 mL of ethanol and 10 mL of water were refluxed under nitrogen for 1 day. It was returned to room temperature, washed with water, extracted with ethyl acetate, and then the organic layer was dried over magnesium sulfate. After filtration, the filtrate was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (ethyl acetate.fwdarw.chloroform:methanol =9:1). 3.4 mmol of 2,5-di(3-pyridyl)-p-xylene was obtained as a colorless solid. Potassium permanganate (20 mmol) and 15 mL of water were added to the obtained solid and heated overnight. It was returned to room temperature and filtered. Then, the residue was washed sufficiently with hot water. Hydrochloric acid was added to the filtrate to adjust the pH to 3. The filtrate was distilled off under reduced pressure, and the obtained solid was washed sufficiently with water and dried to obtain 0.3 g (0.6 mmol) of Organic ligand 10.

[Production Example 10] Synthesis of Organic Ligand 11

[0171] 2,5-Dibromoterephthalic acid (10.0 mmol), 4-hydroxypyridine (40 mmol), copper powder (3.0 mmol), copper iodide (0.8 mmol), 100 mL of dimethylformamide, diazabicycloundecene (60.0 mmol) and 0.2 mL of pyridine were added and heated under reflux overnight. It was returned to room temperature, hydrochloric acid was added thereto, the precipitated solid was filtered, and the residue was washed sufficiently with water. The residue was dried to obtain 3.0 g (6.0 mmol) of Organic ligand 11 as a white solid.

[Production Example 11] Synthesis of Organic ligand 12

[0172] Diethyl 2,5-dibromoterephthalic acid (5.0 mmol), cyclopropylboronic acid (12.0 mmol), palladium acetate (0.05 mmol), potassium phosphate (16 mmol), tricyclohexylphosphine (1.0 mmol), 20 mL of toluene and 1 mL of water was heated under nitrogen at 100° C. overnight. Water was added thereto, the resultant was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and filtered. The filtrate was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (chloroform). Diethyl 2,5-dicyclopropylterephthalate was obtained as a colorless solid. Potassium hydroxide (50 mmol), 50 mL of ethanol, and 20 mL of water were added to the obtained colorless solid and heated at 100° C. for 2 hours. It was returned to room temperature, and concentrated hydrochloric acid was added thereto. It was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and then filtered. The filtrate was distilled off under reduced pressure to obtain 1.7 g (4.2 mmol) of Organic ligand 12.

[Production Example 12] Synthesis of Organic Ligand 13

[0173] Iodine (3.0 mmol) was added to p-di(cyclohexyl)benzene (30 mmol), and the resultant was dissolved in chloroform. Bromine (60 mmol) was added dropwise thereto and stirred for 48 hours. 20% sodium hydroxide was added thereto, and the resultant was extracted with diethyl ether. The extracted solution was dried over magnesium sulfate and filtered. The filtrate was distilled under reduced pressure to obtain 2,5-dibromo-1,4-dicyclohexylbenzene (27 mmol). Copper cyanide (30 mmol) was added to the obtained dibromo form (10 mmol), and the resultant was dissolved in 30 mL of dimethylformamide. The solution was refluxed overnight and returned to the room temperature. Then, 100 mL of aqueous ammonia was added thereto. The precipitated solid was filtered off, and the residue was washed sufficiently with water and dissolved in chloroform. After dried over magnesium sulfate, the solution was filtered, and the filtrate was distilled under reduced pressure. The obtained crude product was recrystallized in hexane to obtain 2,5-dicyano-1,4-dicyclohexylbenzene (9.5 mmol) as a colorless solid. A 10 M sodium hydroxide aqueous solution (75 mmol) was added to the obtained dicyano form (5.0 mmol), and the resultant was dissolved in 50 mL of ethylene glycol. Then the solution was refluxed overnight. After it was returned to the room temperature, 100 mL of water added thereto, and hydrochloric acid was added thereto to adjust the pH to pH 1. The precipitated solid was filtered off and dried sufficiently to obtain 2.2 g (4.6 mmol) of Organic ligand 13.

[Production Example 13] Synthesis of Organic Ligand 15

[0174] Organic ligand 15 was obtained by the same operation as in Production Example 10 except that m-cresol was used instead of 4-hydroxypyridine.

[Production Example 14] Synthesis of Organic Ligand 16

[0175] Organic ligand 16 was obtained by the same operation as in Production Example 10 except that o-cresol was used instead of 4-hydroxypyridine.

[Production Example 15] Synthesis of Organic Ligand 17

[0176] Organic ligand 17 was obtained by the same operation as in Production Example 10 except that p-cresol was used instead of 4-hydroxypyridine.

[Production Example 16] Synthesis of Organic Ligand 18

[0177] Organic ligand 18 was obtained by the same operation as in Production Example 10 except that p-chlorophenol was used instead of 4-hydroxypyridine.

[Production Example 17] Synthesis of Organic Ligand 21

[0178] Organic ligand 21 was obtained by the same operation as in Production Example 10 except that 2-naphthol was used instead of 4-hydroxypyridine.

[Production Example 18] Synthesis of Organic Ligand 22

[0179] Organic ligand 22 was obtained by the same operation as in Production Example 10 except that 4-methoxyphenol was used instead of 4-hydroxypyridine.

[Production Example 19] Synthesis of Organic ligand 23

[0180] Organic ligand 23 was obtained by the same operation as in Production Example 1 except that 3-thienylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 20] Synthesis of Organic Ligand 24

[0181] Organic ligand 24 was obtained by the same operation as in Production Example 1 except that p-chlorophenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 21] Synthesis of Organic Ligand 25

[0182] Organic ligand 25 was obtained by the same operation as in Production Example 1 except that p-methoxyphenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 22] Synthesis of Organic Ligand 26

[0183] Organic ligand 26 was obtained by the same operation as in Production Example 1 except that m-methoxyphenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 23] Synthesis of Organic ligand 27

[0184] Organic ligand 27 was obtained by the same operation as in Production Example 1 except that o-methoxyphenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 24] Synthesis of Organic ligand 28

[0185] Organic ligand 28 was obtained by the same operation as in Production Example 1 except that 3-furylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 25] Synthesis of Organic ligand 29

[0186] Organic ligand 29 was obtained by the same operation as in Production Example 1 except that o-methylthiophenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 26] Synthesis of Organic ligand 30

[0187] Organic ligand 30 was obtained by the same operation as in Production Example 1 except that m-methylthiophenylboronic acid was used instead of o-methylphenylboronic acid.

[Production Example 27] Synthesis of Organic ligand 31

[0188] Organic ligand 31 was obtained by the same operation as in Production Example 1 except that p-methylthiophenylboronic acid was used instead of o-methylphenylboronic acid.

Comparative Example 1

[0189] Terephthalic acid in an amount of 166.7 mg was dissolved in 13 mL of DMF, and 0.28 mL of triethylamine was added thereto. 17 mL of a solution of 557.7 mg of zinc acetate dihydrate in DMF was added dropwise thereto. The resultant was stirred at room temperature for 2.5 hours, and the obtained solid was separated by centrifugation. The supernatant was removed, and the solid was immersed in 20 mL of DMF overnight. Thereafter, the supernatant was removed by centrifugation, and substitution was made using chloroform. The operation of immersing the solid obtained by centrifugation in 20 mL of chloroform and centrifuging the immersed solid again was repeated three times. Thereafter, the solid obtained by centrifugation was dried under vacuum at 150° C. for 5 hours to obtain 142.9 mg of Metal-organic framework A as a white powder.

Comparative Example 2

[0190] DMF in an amount of 50 mL was added to 0.492 g of 2,5-dimethylterephthalic acid and 1.49 g of zinc nitrate hexahydrate and heated in an oven (reaction conditions: 120° C., 24 hours). It was returned to room temperature, and the supernatant was removed. DMF in an amount of 50 mL was added thereto, the supernatant was removed, and the solvent was replaced with chloroform. Chloroform in an amount of 50 mL was added thereto, and immersion was conducted overnight. The solid was subjected to suction filtration, and the obtained solid was dried under vacuum at 150° C. for 5 hours to obtain 0.709 g of Metal-organic framework B.

Example 1-1

[0191] Organic ligand 1 (0.375 mmol), zinc nitrate hexahydrate (0.375 mmol), 1,4-diazabicyclo[2.2.2]octane (0.20 mmol) and 7.5 mL of DMF were stirred for 15 minutes at room temperature and under ultrasonication. Thereafter, the filtrate obtained by centrifugation and filtration was placed in an autoclave and heated in an oven (reaction conditions: 120° C., 66 hours). It was returned to room temperature, the supernatant was discarded, and then the crystal was washed with DMF. Thereafter, the crystal was immersed in DMF overnight. Thereafter, the supernatant was removed and replaced with chloroform. Then the crystal was immersed for 1 day. The step of removing the supernatant after centrifugation was repeated three times. The solid obtained by centrifugation and removal of the supernatant was dried under vacuum at 150° C. to obtain Metal-organic framework 1-1 as a white powder.

Example 1-2 to Example 1-24

[0192] Metal-organic frameworks 1-2 to 1-24 were obtained by the same operation as in Example 1-1 except that

[0193] Organic ligands and solvents shown in Table 2 below were used and the reaction was conducted under the reaction conditions shown in Table 2. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Organic Heating time Example ligand Solvent (hrs.) Property 1-1 1 DMF 66 White powder 1-2 14 DEF 48 Pale orange powder 1-3 11 DMF 48 Pale yellow powder 1-4 5 DMF 48 White powder 1-5 6 DMF 48 White powder 1-6 18 DMF 185 Pale yellow powder 1-7 16 DMF 48 Beige crystal 1-8 15 DMF 48 Bark powder 1-9 9 DMF 48 Off-white crystal 1-10 8 DMF 48 Colorless crystal 1-11 21 DMF 48 Beige powder 1-12 22 DMF 48 Gray solid 1-13 22 DEF 48 Gray solid 1-14 25 DMF 49 Colorless solid 1-15 26 DMF 49 Colorless solid 1-16 27 DMF 49 Colorless solid 1-17 28 DMF 48 Beige solid 1-18 28 DEF 48 Beige solid 1-19 29 DMF 72 Colorless solid 1-20 29 DEF 72 Brown solid 1-21 30 DMF 72 Colorless solid 1-22 30 DEF 72 Pale yellow solid 1-23 31 DMF 72 Colorless solid 1-24 31 DEF 72 Colorless solid

Example 2-1

[0194] Organic ligand 20 (0.5 mmol) was dissolved in 7 mL of DMF. A solution of zinc acetate dihydrate (1.27 mmol) in 8 mL of DMF was added dropwise thereto. The resultant was stirred at room temperature for 2.5 hours, and the obtained solid was separated by centrifugation. The supernatant was removed, and the solid was immersed in 20 mL of DMF overnight. Thereafter, the supernatant was removed by centrifugation, and substitution was made using chloroform. The washing operation of immersing the solid obtained by centrifugation in 20 mL of chloroform overnight and centrifuging the immersed solid again was repeated three times. Thereafter, the solid obtained by centrifugation was dried under vacuum at 150° C. for 5 hours to obtain Metal-organic framework 2-1 as a white powder.

Example 2-2to Example 2-15

[0195] Metal-organic frameworks 2-2 to 2-15 were obtained by the same operation as in Example 2-1 except that Organic ligands and solvents shown in Table 3 below were used and the reaction was conducted under the reaction conditions shown in Table 3. The results are shown in Table 3.

TABLE-US-00003 TABLE 3 Organic Temperature Example ligand (° C.) Property 2-1 20 Room temperature White powder 2-2 3 Room temperature White powder 2-3 12 Room temperature White powder 2-4 13 Room temperature White powder 2-5 11 Room temperature White powder 2-6 16 100 White powder 2-7 15 100 Pale yellow powder 2-8 4 Room temperature White powder 2-9 7 Room temperature White powder 2-10 2 Room temperature White powder 2-11 8 Room temperature White powder 2-12 24 Room temperature Off-white powder 2-13 25 Room temperature Pale yellow powder 2-14 26 Room temperature Colorless powder 2-15 27 Room temperature Colorless powder

Example 3-1

[0196] Organic ligand 20 (1.0 mmol) was dissolved in 13 mL of DMF, and triethylamine (0.0038 mmol) was added thereto. A solution of zinc acetate dihydrate (2.5 mmol) in 17 mL of DMF was added dropwise thereto. The resultant was stirred at room temperature for 2.5 hours, and the obtained solid was separated by centrifugation. The supernatant was removed, and the solid was immersed in 20 mL of DMF overnight. Thereafter, the supernatant was removed by centrifugation, and substitution was made using chloroform. The washing operation of immersing the solid obtained by centrifugation in 20 mL of chloroform overnight and centrifuging the immersed solid again was repeated three times. Thereafter, the solid obtained by centrifugation was dried under vacuum at 150° C. for 5 hours to obtain Metal-organic framework 3-1 as a white powder.

Example 3-2 to Example 3-12

[0197] Metal-organic frameworks 3-2 to 3-12 were obtained by the same operation as in Example 3-1 except that Organic ligands and solvents shown in Table 4 below were used and the reaction was conducted under the reaction conditions shown in Table 4. The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Organic Heating time Example ligand (hrs.) Property 3-1 20 2.5 White powder 3-2 12 2.5 White powder 3-3 13 2.5 White powder 3-4 1 2.5 White powder 3-5 11 2.5 White powder 3-6 4 2.5 White powder 3-7 7 2.5 White powder 3-8 8 20 White powder 3-9 24 2.5 Off-white powder 3-10 25 2.5 Pale yellow powder 3-11 26 17 Colorless powder 3-12 27 2.5 Colorless powder

Example 4-1

[0198] DMF in an amount of 10 mL was added to Organic ligand 14 (0.3 mmol) and zinc nitrate hexahydrate (0.4 mmol) and stirred for 5 minutes. Triethylamine (0.0068 mmol) was added dropwise thereto and stirred at room temperature for 5 minutes. After still standing for 20 minutes, the resultant was centrifuged for 10 minutes to remove the supernatant. DMF in an amount of 10 mL was added to the residue, and the resultant was centrifuged again for 10 minutes to remove the supernatant. After immersion in DMF overnight, the resultant was centrifuged for 10 minutes to remove the supernatant, and then 10 mL of chloroform was added thereto. The washing operation of immersing the solid obtained by centrifugation in 20 mL of chloroform overnight and centrifuging the immersed solid again was repeated three times. Thereafter, the solid obtained by centrifugation was dried under vacuum at 150° C. for 5 hours to obtain Metal-organic framework 4-1 as a pale yellow powder.

Example 4-2 to Example 4-20

[0199] Metal-organic frameworks 4-2 to 4-20 were obtained by the same operation as in Example 4-1 except that Organic ligands shown in Table 5 below were used. The results are shown in Table 5.

TABLE-US-00005 TABLE 5 Example Organic ligand Property 4-1 14 Pale yellow powder 4-2 12 White powder 4-3 1 White powder 4-4 18 Pale green powder 4-5 5 White powder 4-6 6 White powder 4-7 16 Pale yellow powder 4-8 15 Yellow powder 4-9 3 White powder 4-10 20 White powder 4-11 17 White powder 4-12 2 White powder 4-13 9 Pale gray powder 4-14 8 White powder 4-15 21 Green bark powder 4-16 24 Beige powder 4-17 25 Colorless powder 4-18 26 Colorless powder 4-19 27 Colorless powder 4-20 11 Colorless powder

Example 5-1

[0200] DMF in an amount of 3.8 mL was added to Organic ligand 14 (0.175 mmol) and zinc nitrate hexahydrate (0.352 mmol) and heated in an oven (reaction conditions: 100° C., 161 hours). It was returned to room temperature and centrifuged, and then the supernatant was removed. DMF in an amount of 10 mL was added thereto, the resultant was centrifuged, and then the solvent was removed and replaced with chloroform. Chloroform in an amount of 10 mL was added thereto, and immersion was conducted overnight. After removal of the chloroform by centrifugation, the residue was dried under vacuum at 150° C. for 5 hours to obtain Metal-organic framework 5-1 as a pale orange crystal.

Example 5-2 to Example 5-86

[0201] Metal-organic frameworks 5-2 to 5-86 were obtained by the same operation as in Example 5-1 except that Organic ligands and solvents shown in Table 6 below were used and the reaction was conducted under the reaction conditions shown in Table 6. The results are shown in Table 6.

TABLE-US-00006 TABLE 6 Temperature Heating time Example Organic ligand Solvent (° C.) (hrs.) Property 5-1 14 DMF 100 161 Pale orange crystal 5-2 14 DEF 100 72 5-3 3 DMF 120 24 5-4 3 DEF 120 24 5-5 19 DMF 120 24 Bark powder 5-6 2 DMF 120 24 5-7 2 DEF*.sup.1 90 24 5-8 2 DEF*.sup.1 120 24 5-9 12 DMF 90 72 Colorless crystal 5-10 12 DEF 90 24 Pale bark crystal 5-11 13 DMF 90 24 Colorless crystal 5-12 13 DMF 120 24 Colorless crystal 5-13 13 DEF 120 24 Pale bark crystal 5-14 10 DMF 120 24 White powder 5-15 1 DMF 120 24 White solid 5-16 1 DEF 120 24 Bark solid 5-17 17 DEF 120 24 Bark solid 5-18 5 DMF 120 24 Bark solid 5-19 5 DEF 120 24 Bark solid 5-20 6 DMF 120 24 Colorless crystal 5-21 6 DEF 120 24 Off-white crystal 5-22 14 DMF 120 28 Orange crystal 5-23 4 DEF 120 24 Colorless crystal 5-24 16 DMF 120 24 Off-white crystal 5-25 16 DEF 120 24 Pale bark crystal 5-26 16 DEF 90 24 Light gray yellow crystal 5-27 15 DMF 120 24 Pale bark crystal 5-28 15 DMF 90 240 Pale yellow crystal 5-29 15 DEF 120 24 Bark crystal 5-30 15 DEF 90 140 Light gray yellow crystal 5-31 7 DMF 90 24 White solid 5-32 7 DMF 120 24 White solid 5-33 7 DEF 90 48 White solid 5-34 7 DEF 120 24 White solid 5-35 3 DEF 90 75 Light gray yellow crystal 5-36 9 DMF 120 24 White crystal 5-37 9 DEF 120 24 Light gray yellow crystal 5-38 9 DEF 90 24 Colorless crystal 5-39 8 DMF 120 24 Colorless crystal 5-40 8 DMF 90 144 Colorless crystal 5-41 8 DEF 120 24 Pale yellow crystal 5-42 8 DEF 90 72 Colorless crystal 5-43 21 DEF 120 48 Bark crystal 5-44 22 DMF 90 48 Gray solid 5-45 22 DMF 120 48 Gray solid 5-46 22 DEF 90 48 Gray solid 5-47 22 DEF 120 48 Yellow bark solid 5-48 23 DMF 90 24 Pale yellow crystal 5-49 23 DMF 120 24 Colorless crystal 5-50 23 DEF 90 24 Yellow crystal 5-51 23 DEF 120 24 Orange crystal 5-52 24 DMF 120 24 Bark crystal + colorless solid 5-53 24 DMF 90 24 Colorless solid 5-54 24 DEF 90 24 Colorless solid 5-55 24 DEF 120 24 Pale bark solid 5-56 25 DMF 120 24 Colorless crystal 5-57 25 DMF 90 48 Colorless crystal 5-58 25 DEF 120 24 Pale yellow crystal 5-59 25 DEF 90 48 Off-white crystal 5-60 26 DMF 120 24 Colorless crystal 5-61 26 DMF 90 48 Colorless crystal 5-62 26 DEF 120 24 Pale yellow crystal 5-63 26 DEF 90 48 Pale yellow crystal 5-64 27 DMF 120 24 Colorless crystal 5-65 27 DMF 90 48 Colorless crystal 5-66 27 DEF 120 24 Beige crystal 5-67 28 DMF 90 48 Bark solid 5-68 28 DMF 120 48 Bark solid 5-69 28 DEF 90 48 Orange solid 5-70 28 DEF 120 48 Orange solid 5-71 29 DMF 90 72 Colorless solid 5-72 29 DMF 120 72 Colorless solid 5-73 29 DEF 90 72 Pale yellow solid 5-74 29 DEF 120 72 Brown solid 5-75 30 DMF 90 72 Colorless solid 5-76 30 DMF 120 72 Colorless solid 5-77 30 DEF 90 72 Pale brown solid 5-78 30 DEF 120 72 Bark solid 5-79 31 DMF 90 72 Pale yellow solid 5-80 31 DMF 120 72 Pale yellow solid 5-81 31 DEF 90 72 Yellow solid 5-82 31 DEF 120 72 Bark solid 5-83 11 DMF 120 24 Colorless powder 5-84 11 DMF 90 24 Colorless powder 5-85 11 DEF 120 24 Off-white powder 5-86 11 DEF 90 24 Off-white powder *1: DEF was added so as to achieve 2-fold dilution in comparison with that of Example 5-1.

Example 6-1

[0202] 3 mL of a solution of Organic ligand 12 (0.38 mmol) in DMF and 2.5 mL of 1,4-diazabicyclo[2.2.2]octane (0.2 mmol) in DMF were slowly added dropwise to a solution of zinc acetate dihydrate (0.38 mmol) in 2 mL in DMF. After stirring at room temperature for 2.5 hours, the mixture was centrifuged to remove the supernatant. DMF was added thereto, and after immersion of overnight, the supernatant was removed and replaced with chloroform. Chloroform in an amount of 10 mL was added thereto, and the resultant was immersed for 1 day. The operation of centrifugation, removal of the solvent, addition of chloroform again, immersion overnight, and removal of the supernatant after centrifugation was repeated three times. The solid obtained by centrifugation and removal of the supernatant was dried under vacuum at 150° C. to obtain Metal-organic framework 6-1 as a colorless crystal.

Example 7-1

[0203] THF in an amount of 9 mL and water in an amount of 1 mL were added to 0.152 g of Organic ligand 25 and 0.233 g of nickel nitrate hexahydrate and heated in an oven (reaction conditions: 100° C., 48 hours). It was returned to room temperature, centrifuged and decanted to obtain a solid. The operation of adding DMF to the solid and centrifuging and decanting it was repeated three times. Then DMF was added thereto to immerse the solid overnight. The operation of removing the supernatant, adding chloroform to the solid, and centrifuging and decanting it was repeated three times. The solvent was replaced with chloroform, and chloroform was added thereto to immerse the solid overnight. The solid obtained by decanting the solid was dried under vacuum at 150° C. for 5 hours to obtain 0.178 g of Metal-organic framework 7-1.

Example 7-2 to Example 7-17

[0204] Metal-organic frameworks 7-2 to 7-17 were obtained in the same operation as in Example 4-1 except that Organic ligands shown in Table 7 below and the reaction was conducted under the reaction conditions shown in Table 7. The results are shown in Table 7.

TABLE-US-00007 TABLE 7 Organic Heating time Example ligand (hrs.) Property 7-1 25 48 Brown bark crystal 7-2 26 48 Pale green + ocherous powder 7-3 27 48 Yellow bark crystal 7-4 14 24 Bark solid 7-5 11 24 Pale green crystal 7-6 3 48 Pale bark solid 7-7 9 48 Brown powder 7-8 13 48 Yellow bark powder 7-9 18 48 Bark powder 7-10 2 48 Red bark powder 7-11 6 48 Beige powder 7-12 5 48 Yellow powder 7-13 16 48 Bark powder 7-14 15 49 Bark powder 7-15 17 49 Bark powder 7-16 8 48 Pale green + ocherous powder 7-17 1 48 Red bark powder

Example 8-1

[0205] 0.114 g of Organic ligand 25, 0.0702 g of zirconium chloride, 0.0625 g of water, 0.5406 g of acetic acid and 4 mL of DMF were stirred for 5 minutes at room temperature and under ultrasonication. Thereafter, the mixture was heated in an oven (reaction conditions: 120° C., 24 hours). It was returned to room temperature, centrifuged and decanted to obtain a solid. The operation of adding DMF to the solid and centrifuging and decanting it was repeated three times. The supernatant was removed, and DMF was added thereto to immerse the solid overnight. The operation of decanting the immersed solid after centrifugation, adding acetone to the obtained solid, and centrifuging and decanting it was repeated three times. The supernatant was removed, and acetone was added thereto to immerse the solid overnight. The solid obtained by centrifugation and decantation was dried under vacuum at 150° C. for 5 hours to obtain 0.0826 g of Metal-organic framework 8-1.

Example 8-2 to Example 8-10

[0206] Metal-organic frameworks 8-2 to 8-10 were obtained by the same operation as in Example 8-1 except that Organic ligands shown in Table 8 below were used. The results are shown in Table 8.

TABLE-US-00008 TABLE 8 Example Organic ligand Property 8-1 25 Colorless powder 8-2 26 White powder 8-3 14 Yellow solid 8-4 18 Bark solid 8-5 3 Colorless powder 8-6 16 Pale yellow solid 8-7 15 Pale yellow powder 8-8 17 Beige solid 8-9 2 Colorless powder 8-10 8 Colorless powder

Example 9-1

[0207] Organic ligand 25 in an amount of 0.0759 g, 0.0484 g of copper nitrate trihydrate and 4 mL of DMF were added and stirred, and then the mixture was filtered. Thereafter, the mixture was heated in an oven (reaction conditions: 120° C., 24 hours). It was returned to room temperature, centrifuged and decanted to obtain a solid.

[0208] The operation of adding DMF to the solid and centrifuging and decanting it was repeated three times. Then DMF was added thereto, and the solid was immersed overnight. The supernatant was removed, and the solvent was replaced with chloroform. The operation of addition of chloroform, washing and filtration under pressure was repeated three times, and chloroform was added thereto to immerse the solid overnight. The solid was subjected to filtration under pressure, and the obtained solid was dried under vacuum at 150° C. for 5 hours to obtain 0.0670 g of Metal-organic framework 9-1.

Example 9-2 to Example 9-32

[0209] Metal-organic frameworks 9-2 to 9-32 were obtained by the same operation as in Example 9-1 except that Organic ligands shown in Table 9 below were used. The results are shown in Table 9.

TABLE-US-00009 TABLE 9 Heating Organic Heating temperature Example ligand time (hrs.) (° C.) Solvent Property 9-1 25 24 120 DMF Light blue powder 9-2 26 24 120 DMF Light blue powder 9-3 27 24 120 DMF Light blue powder 9-4 14 24 120 DMF Emerald green crystal 9-5 14 24 90 DMF Emerald green crystal 9-6 14 24 120 DEF Green crystal 9-7 14 24 90 DEF Light blue solid 9-8 11 24 120 DMF Light blue solid 9-9 11 24 90 DMF Light blue solid 9-10 11 24 120 DEF Light blue + yellow green solid 9-11 11 24 90 DEF Colorless solid 9-12 1 24 120 DMF Blue solid 9-13 1 24 90 DMF Light blue solid 9-14 1 24 120 DEF Blue solid 9-15 1 24 90 DEF Light blue solid 9-16 3 43 120 DMF Light blue solid 9-17 3 43 90 DMF Light blue solid 9-18 3 43 120 DEF Light blue solid 9-19 3 43 90 DEF Light blue solid 9-20 2 24 120 DMF Light blue solid 9-21 2 24 90 DMF Light blue solid 9-22 2 24 120 DEF Light blue solid 9-23 2 24 90 DEF Light blue solid 9-24 9 48 120 DMF Dark blue powder 9-25 9 48 90 DMF Light blue powder 9-26 9 48 120 DEF Dark blue powder 9-27 9 48 90 DEF Dark light blue solid 9-28 13 40 120 DMF Purple powder 9-29 16 24 120 DMF Dark blue powder 9-30 15 24 120 DMF Dark blue powder 9-31 18 40 120 DMF Light blue powder 9-32 11 0.5 RT DMF Colorless powder

Examples 10-1 and 10-2

[0210] Organic ligand 11 in an amount of 0.1839 g, 0.0521 g of copper acetate monohydrate, 0.1098 g of acetic acid and 10 mL of DMF were added to a vial and ultrasonicated for 5 minutes. Thereafter, the mixture was heated in an oven (reaction conditions: 70° C., 7 days). When the mixture was returned to room temperature, light blue and white solids were obtained. The solids were visually separated and centrifuged, and then decanted to obtain each solid. DMF was added to each solid to immerse each solid overnight. DMF was removed by centrifugation and decantation, and the solvent was replaced with chloroform. For the blue solid, this step was repeated three times. The obtained solid was dried under vacuum at 150° C. for 5 hours to obtain 0.0538 g of Metal-organic framework 10-1. For the white solid, the operation of centrifugation and filtration under pressure was repeated three times. Then, the obtained solid was dried under vacuum at 150° C. for 5 hours to obtain 0.0258 g of Metal-organic framework 10-2.

Measurement of BET Specific Surface Area and Measurement Of Hydrogen Storage Capacity

[0211] The BET specific surface area and the hydrogen storage capacity at 77 K and atmospheric pressure were measured for some of Metal-organic frameworks obtained. The hydrogen storage amount at 298 K and 10 MPa was also measured for some of Metal-organic frameworks.

[0212] The BET specific surface area and the hydrogen storage capacity at 77 K and atmospheric pressure were measured with a gas adsorption measurement device, Tristar-II (manufactured by Micromeritics Instrument Corporation)

[0213] The BET specific surface area was calculated according to the following procedure. About 50 mg of each of Metal-organic frameworks was placed inside a glass cell. The pressure inside the glass cell was reduced to vacuum at a temperature of 135° C. and the inside of the glass cell was dried for 6 hours. The glass cell was attached to the gas adsorption measurement device and immersed in a temperature-controlled bath containing liquid nitrogen. The pressure of nitrogen contained in the glass cell was gradually increased. The measurement was carried out until the pressure of nitrogen introduced into the glass cell reached 1.0×10.sup.5 Pa.

[0214] The hydrogen storage capacity at 77K and a normal pressure was calculated according to the following procedure. After the measurement for nitrogen, the gas type was changed to hydrogen to carry out the measurement. The pressure of hydrogen contained in the glass cell was gradually increased. The measurement was carried out until the pressure of hydrogen introduced into the glass cell reached 1.0×10.sup.5 Pa.

[0215] The results of the BET specific surface areas measured were shown in Table 10.

[0216] The hydrogen storage capacities measured at 77 K and atmospheric pressure are shown in Table 11.

TABLE-US-00010 TABLE 10 Metal-organic BET specific Metal-organic BET specific Metal-organic BET specific framework surface area framework surface area framework surface area number (m.sup.2/g) number (m.sup.2/g) number (m.sup.2/g) 1-9  601 5-4  1028 5-66 907 2-1  733 5-6  560 5-72 945 2-2  530 5-7  555 8-1  511 2-3  1187 5-8  655 8-2  442 2-4  616 5-9  1659 8-3  411 2-5  1939 5-10 1591 8-4  419 2-6  810 5-11 1013 8-5  591 2-7  755 5-12 807 8-8  466 2-8  522 5-13 712 8-9  665 2-9  531 5-15 990 8-10 679 2-10 653 5-16 984 B 426 2-11 445 5-17 448 2-14 653 5-18 771 3-1  870 5-19 895 3-2  563 5-20 720 3-3  700 5-21 846 3-4  481 5-22 982 3-5  2019 5-23 786 3-6  486 5-24 586 3-7  551 5-25 606 3-8  533 5-26 884 3-12 449 5-27 872 4-1  963 5-28 909 4-2  1322 5-29 752 4-3  1057 5-30 538 4-5  851 5-31 729 4-6  773 5-32 743 4-7  580 5-33 824 4-8  597 5-34 714 4-9  437 5-35 1063 4-10 961 5-36 1294 4-11 483 5-37 851 4-12 706 5-38 746 4-13 830 5-39 697 4-14 637 5-41 972 4-17 690 5-42 753 4-18 656 5-59 723 4-19 606 5-60 545 5-1  1107 5-62 670 5-2  991 5-64 921 5-3  874 5-65 889

TABLE-US-00011 TABLE 11 Metal-organic Hydrogen storage Metal-organic Hydrogen storage framework number capacity (wt %) framework number capacity (wt %) 2-3  1.108 5-13 1.177 2-5  1.564 5-15 1.284 2-6  1.149 5-16 1.267 2-7  1.042 5-18 1.043 2-14 1.018 5-19 1.158 3-3  1.071 5-21 1.137 3-5  1.676 5-22 1.151 4-1  1.122 5-26 1.188 4-2  1.262 5-27 1.162 4-3  1.394 5-28 1.161 4-5  1.116 5-29 1.028 4-6  1.021 5-35 1.393 4-17 1.130 5-40 1.226 4-18 1.068 5-41 1.337 5-1  1.242 5-42 1.530 5-2  1.072 5-59 1.265 5-3  1.298 5-62 1.076 5-4  1.496 5-64 1.337 5-9  1.541 5-65 1.306 5-10 1.486 5-66 1.316 5-11 1.568 5-72 1.060 5-12 1.283 A 1.111

INDUSTRIAL APPLICABILITY

[0217] The metal-organic framework of the present invention can store gases such as hydrogen and nitrogen at a practical level. Consequently, the metal-organic framework can make hydrogen to be utilized more easily, toward the advent of a hydrogen energy-based society.