Metal-organic frameworks using terphenyl-based carboxylate ions as ligands

Abstract

A problem addressed by the present invention is to provide a novel metal-organic framework with a dicarboxylic acid having a terphenyl skeleton as an organic ligand, and a gas storage method using the same.　A metal-organic framework obtained by bonding a carboxylic acid ion represented by formula (I) and a polyvalent metal ion. (In formula (I), R1 and R2 each independently represent a hydroxy group, a substituted or unsubstituted C1-6 alkyl group, etc. R10 and R11 each independently represent a substituted or unsubstituted C1-6 alkyl group, etc. R20 represents a substituted or unsubstituted C1-6 alkyl group, etc. However, a carboxy group (COOH) and carboxylic acid ion group (COO-) are excluded as substituents on R1, R2, R3, R4, R5, R6, R7, R8, R10, R11, and R20. Also, R10 and R11 may not simultaneously be methyl groups.)

Description

[Technical field]

[0001] The present invention relates to a novel metal-organic framework having a carboxylate ion having a terphenyl skeleton as a ligand and a method for storing gas using the same. This application claims priority to Japanese Patent Application No. 2020-032043 filed on February 27, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Metal-organic frameworks (hereinafter sometimes referred to as "MOFs") are solid substances with polymeric structures that have internal spaces (i.e., pores) created by combining metal ions with bridging organic ligands that link them, and have attracted great interest over the past decade as porous materials with functions such as gas storage and separation. There have been many studies using terephthalic acid as an organic ligand, and it is known that MOF-5, which is obtained by a solvothermal method using Zn(NO3)2·6H2O in DMF using terephthalic acid as a bridging organic ligand, can store 7.1% by mass of hydrogen relative to MOF-5 at a temperature of 77 K and 4 MPa (see Patent Document 1 and Non-Patent Documents 1-3).

[0003] On the other hand, the surface area obtained by heating zirconium chloride and terphenyl dicarboxylic acid in dimethylformamide is 4000 m 2 It is known that MOFs with a capacity of 100000000 / g can store gases such as hydrogen, methane, and acetylene (see Patent Document 2).

[0004] In addition, by heating a dicarboxylic acid represented by the following formula and Fe2CoO(CH3COO)6 or Fe3O(CH3COO)6 in N-methylpyrrolidone in the presence of acetic acid at 150°C for 24 hours, an MOF is obtained as dark brown crystals, and it is known that this MOF can store gases such as hydrogen, methane, carbon dioxide, and nitrogen (see Patent Document 3).

[0005] [ka] [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent Publication No. 2010-75123 [Patent Document 2] International Publication No. 2009-133366 [Patent Document 3] International Publication No. 2015-079229 [Non-patent literature]

[0007] [Non-Patent Document 1] H. Li, M. Eddaudi, M. O'Keefe, OM Yaghi, Nature, 402, 276(1999) [Non-Patent Document 2] M. Eddaudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keefe, OM Yaghi, Science 2002, 295(5554), 469. [Non-Patent Document 3] S. Kaye, A. Daily, OM Yaghi, J. Long, J. Am. Chem. Soc. 2007, 129(46), 14176. Summary of the Invention [Problem to be solved by the invention]

[0008] It is known that the structure of MOFs changes significantly depending on the metal species, ligands, and reaction conditions used. There are few reports on MOFs that use dicarboxylic acids with a terphenyl skeleton as organic ligands. An objective of the present invention is to provide a novel MOF having a dicarboxylic acid having a terphenyl skeleton as an organic ligand, and a gas storage method using the same. [Means for solving the problem]

[0009] As a result of intensive research aimed at solving the above problems, the present inventors have found novel MOFs that can be obtained by using compounds having specific substituents at specific positions of the terphenyl skeleton as organic ligands. They have also found that these novel MOFs have high hydrogen storage capacity, and have completed the present invention.

[0010] That is, the present invention is as follows, which is specified by the items shown below. [1] A metal organic framework formed by bonding a carboxylate ion represented by formula (I) and a polyvalent metal ion. [ka] (In formula (I), R 1 and R 2 each independently represents a hydroxy group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted and a C6-10 arylthio group having a substituent, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (II). [ka] (In formula (II), R 3 and R 4 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates the bonding position.) n is R 1 and is 0, 1, 2, 3, or 4; when n is 2 or more, there are multiple R 1 may be the same or different from each other. m is R 2 and is 0, 1, 2, 3, or 4; when m is 2 or more, a plurality of R 2 may be the same or different from each other. R 10 and R 11 each independently represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted C and R represents an unsubstituted or substituted C6-10 arylthio group, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (III). [ka] (In formula (III), R 5 and R6 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates the bonding position.) R 20 is an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted C6-1 arylthio group, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (IV). [ka] (In formula (IV), R 7 and R 8 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates the bonding position.) q is R 20 and is 0, 1 or 2; when q is 2, R 20 may be the same or different from each other. However, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 20 The above substituents include carboxyl groups (COOH) and carboxylate groups (COO - ) except for R 10 and R 11 but not simultaneously a methyl group.) [2] The metal organic structure according to [1], wherein the carboxylate ion represented by formula (I) is a carboxylate ion represented by formula (V): [ka] (In the formula, R 1 , R 2 , R 10 , R 11 , n and m have the same meanings as in formula (I). [3] The metal organic structure according to [1] or [2], wherein the polyvalent metal ion is an ion of at least one metal selected from the group consisting of metals of groups 2 to 13 of the periodic table. [4] The metal organic structure according to any one of [1] to [3], wherein the polyvalent metal ion is an ion of at least one metal selected from Zn, Fe, Co, Ni, Cu, Al, Zr, Ti, Cr, and Mg. [5] The metal organic structure according to any one of [1] to [4], further comprising an organic ligand other than the carboxylate ion represented by formula (I) as a constituent component. [6] A gas storage method comprising the steps of contacting a gas with the metal-organic framework according to any one of [1] to [5] and adsorbing or occluding the gas inside the metal-organic framework. Effect of the Invention

[0011] The MOF of the present invention is novel, and by using the MOF of the present invention, gases such as hydrogen, carbon dioxide, and nitrogen can be stored. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The MOF of the present invention is an MOF in which a polyvalent metal ion and a dicarboxylate ion having a terphenyl skeleton are bonded together.

[0013] The polyvalent metal ion used in the present invention is not particularly limited as long as it is an ion of a divalent or higher metal, but is preferably an ion of at least one metal selected from the group consisting of metals of groups 2 to 13 of the periodic table, more preferably an ion of at least one metal selected from Zn, Fe, Co, Ni, Cu, Al, Zr, Ti, Cr, and Mg, and further preferably an ion of at least one metal selected from Co, Ni, Cu, Zr, Ti, Cr, and Zn, and these can be used alone or in combination of two or more.

[0014] These polyvalent metal ions are supplied in the form of various salts, such as zinc nitrate (Zn(NO3)2·xH2O), titanium nitrate (Ti(NO3)4·xH2O), cobalt nitrate (Co(NO3)2·xH2O), iron(III) nitrate (Fe(NO3)3·xH2O), iron(II) nitrate (Fe(NO3)2·xH2O), nickel(II) nitrate (Ni(NO3)2·xH2O), copper(II) nitrate (Cu(NO3)2·xH2O); zinc chloride (ZnCl2·xH2O), titanium chloride (TiCl4·xH2O), and zirconium chloride (ZrCl4·xH2O). , cobalt chloride (CoCl2·xH2O), iron(III) chloride (FeCl3·xH2O), iron(II) chloride (FeCl2·xH2O); zinc acetate (Zn(CH3COO)2·xH2O), titanium acetate (Ti(CH3COO)4·xH2O), zirconium acetate (Zr(CH3COO)4·xH2O), cobalt acetate (Co(CH3COO)2·xH2O), iron(III) acetate (Fe(CH3COO)3·xH2O), iron(II) acetate (Fe(CH3COO)2·xH2O); zinc sulfate (ZnSO4·xH2 O), titanium sulfate (Ti(SO4)2·xH2O), zirconium sulfate (Zr(SO4)2·xH2O), cobalt sulfate (CoSO4·xH2O), iron(III) sulfate (Fe2(SO4)3·xH2O), iron(II) sulfate (FeSO4·xH2O); zinc hydroxide (Zn(OH)2·xH2O), titanium hydroxide (Ti(OH)4·xH2O), zirconium hydroxide (Zr(OH)4·xH2O), cobalt hydroxide (Co(OH)2·xH2O), iron(III) hydroxide (Fe(OH)3·xH2O), iron hydroxide (II) (Fe(OH)2·xH2O); zinc bromide (ZnBr2·xH2O), titanium bromide (TiBr4·xH2O), zirconium bromide (ZrBr4·xH2O), cobalt bromide (CoBr2·xH2O), iron (III) bromide (FeBr3·xH2O), iron (II) bromide (FeBr2·xH2O); zinc carbonate (ZnCO3·xH2O), cobalt carbonate (CoCO3·xH2O), iron (III) carbonate (Fe2(CO3)3·xH2O); zirconium oxide chloride (ZrOCl2·xH2O), etc. can be mentioned. Note that x is a number from 0 to 12. These can be used alone or in combination of two or more.

[0015] The carboxylate ion having a terphenyl skeleton used in the present invention is represented by the following formula (I). [ka]

[0016] In formula (I), R 1 and R 2 each independently represents a hydroxy group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted and a C6-10 arylthio group having a substituent, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (II). n is R 1 and is 0, 1, 2, 3, or 4; when n is 2 or more, there are multiple R 1 may be the same or different from each other. m is R 2 and is 0, 1, 2, 3, or 4; when m is 2 or more, a plurality of R 2 may be the same or different from each other.

[0017] R 1 and R 2The C1-6 alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, an t-butyl group, an i-pentyl group, a neopentyl group, a 2-methyl-n-butyl group, and an i-hexyl group.

[0018] R 1 and R 2 Examples of the C3-8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cubanyl group.

[0019] R 1 and R 2 The C6-10 aryl group may be either monocyclic or polycyclic, and as long as at least one ring of the polycyclic aryl group is an aromatic ring, the remaining rings may be any of saturated alicyclic rings, unsaturated alicyclic rings, or aromatic rings. Specific examples include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.

[0020] R 1 and R 2 The 3- to 6-membered heterocyclyl group contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms as ring constituent atoms. The heterocyclyl group may be either a monocyclic or polycyclic. As for the polycyclic heterocyclyl group, as long as at least one ring is a heterocyclic ring, the remaining rings may be any of saturated alicyclic, unsaturated alicyclic or aromatic hydrocarbon rings. Examples of the 3- to 6-membered heterocyclyl group include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.

[0021] Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuryl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, and a dioxanyl group.

[0022] Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, a tetrazolyl group, an indonyl group, an isoindolinyl group, an indolizinyl group, a benzimidazolyl group, and a carbazolyl group. Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazyl group, a pyrimidyl group, a pyridazyl group, a triazyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a cinnolinyl group, a quinazolyl group, a phthalazinyl group, an acridinyl group, a naphthazinyl group, and a phenazinyl group.

[0023] R 1 and R 2 Examples of the C1-6 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, and a t-butoxy group. R 1 and R 2 Examples of the C6-10 aryloxy group include a phenoxy group, a naphthyloxy group, an azulenyloxy group, an indenyloxy group, an indanyloxy group, and a tetralinyloxy group.

[0024] R 1 and R 2 Examples of the heteroaryloxy group include a furyloxy group, a thiazolyloxy group, and a pyridyloxy group. R 1 and R 2 Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0025] R 1 and R 2 Examples of the C1-6 alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, an s-butylthio group, and a t-butylthio group. R 1 and R 2Examples of the C6-10 arylthio group include a phenylthio group, a naphthylthio group, an azulenylthio group, an indenylthio group, an indanylthio group, and a tetralinylthio group. R 1 and R 2 Examples of the heteroarylthio group include a furylthio group, a thiazolylthio group, and a pyridylthio group.

[0026] R 1 and R 2 Examples of the C1-6 alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, and a t-butylsulfinyl group. R 1 and R 2 Examples of the C6-10 arylsulfinyl group include a phenylsulfinyl group, a naphthylsulfinyl group, an azulenylsulfinyl group, an indenylsulfinyl group, an indanylsulfinyl group, and a tetralinylsulfinyl group. R 1 and R 2 Examples of the heteroarylsulfinyl group include a furylsulfinyl group, a thiazolylsulfinyl group, and a pyridylsulfinyl group.

[0027] R 1 and R 2 Examples of the C1-6 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a t-butylsulfonyl group. R 1 and R 2 Examples of the C6-10 arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, an azulenylsulfonyl group, an indenylsulfonyl group, an indanylsulfonyl group, and a tetralinylsulfonyl group. R 1 and R 2 Examples of the heteroarylsulfonyl group include a furylsulfonyl group, a thiazolylsulfonyl group, and a pyridylsulfonyl group.

[0028] The group represented by formula (II) is shown below. [ka] In formula (II), R 3 and R 4 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates a bonding position.

[0029] R 3 and R 4 The C1-6 alkyl group and the C6-10 aryl group of R 1 and R 2 Examples of the examples are the same as those given in the above. R 3 and R 4 Examples of the C1-6 alkylcarbonyl group include an acetyl group, a n-propionyl group, an isopropionyl group, a n-butyryl group, an isobutyryl group, a pivaloyl group, and a n-pentanoyl group. R 3 and R 4 Examples of the C6-10 arylcarbonyl group include a benzoyl group, a 1-naphthylcarbonyl group, and a 2-naphthylcarbonyl group. Examples of the group represented by formula (II) include an amino group, a methylamino group, a dimethylamino group, an ethyl-i-propylamino group, an anilino group, a diphenylamino group, an acetylamino group, and a benzoylamino group.

[0030] In formula (I), R 10 and R 11each independently represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted C and R represents an unsubstituted or substituted C6-10 arylthio group, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (III).

[0031] R 10 and R 11 The C1-6 alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, an t-butyl group, an i-pentyl group, a neopentyl group, a 2-methyl-n-butyl group, and an i-hexyl group.

[0032] R 10 and R 11 Examples of the C3-8 cycloalkyl group, C6-10 aryl group, 3- to 6-membered heterocyclyl group, C1-6 alkoxy group, C6-10 aryloxy group, heteroaryloxy group, halogeno group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group, heteroarylsulfinyl group, C1-6 alkylsulfonyl group, C6-10 arylsulfonyl group and heteroarylsulfonyl group include R1 and R 2 Examples of the above-mentioned examples are the same as those exemplified above.

[0033] The group represented by formula (III) is shown below. [ka] In formula (III), R 5 and R 6 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates a bonding position. In formula (III), R 5 and R 6 As for R 3 and R 4 Examples of the group represented by formula (III) include the same as those exemplified for the group represented by formula (II).

[0034] In formula (I), R 20is an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted 3-6 membered heterocyclyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6-10 aryloxy group, an unsubstituted or substituted heteroaryloxy group, a halogeno group, an unsubstituted or substituted C1-6 alkylthio group, an unsubstituted or substituted C6-1 arylthio group, an unsubstituted or substituted heteroarylthio group, an unsubstituted or substituted C1-6 alkylsulfinyl group, an unsubstituted or substituted C6-10 arylsulfinyl group, an unsubstituted or substituted heteroarylsulfinyl group, an unsubstituted or substituted C1-6 alkylsulfonyl group, an unsubstituted or substituted C6-10 arylsulfonyl group, an unsubstituted or substituted heteroarylsulfonyl group, a cyano group, a nitro group, or a group represented by formula (IV). q is R 20 and is 0, 1 or 2; when q is 2, R 20 may be the same or different from each other.

[0035] R 20 Examples of the C1-6 alkyl group, C3-8 cycloalkyl group, C6-10 aryl group, 3- to 6-membered heterocyclyl group, C1-6 alkoxy group, C6-10 aryloxy group, heteroaryloxy group, halogeno group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group, heteroarylsulfinyl group, C1-6 alkylsulfonyl group, C6-10 arylsulfonyl group and heteroarylsulfonyl group include R 1 and R 2 Examples of the above-mentioned examples are the same as those exemplified above.

[0036] The group represented by formula (IV) is shown below. [ka] In formula (IV), R 7 and R 8 each independently represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted C1-6 alkylcarbonyl group, or an unsubstituted or substituted C6-10 arylcarbonyl group. * indicates a bonding position. In formula (IV), R 7 and R 8 As for R 3 and R 4 Examples of the group represented by formula (IV) include the same as those exemplified for the group represented by formula (II).

[0037] In the present invention, the term "unsubstituted" means that only the core group is present. When only the name of the core group is described, it means "unsubstituted" unless otherwise specified. On the other hand, the term "substituted" means that any hydrogen atom of the core group is substituted with a group having the same or different structure as the core group. Thus, a "substituent" is another group bonded to the core group. The number of substituents may be one or more. The two or more substituents may be the same or different, and the two or more substituents may be bonded to the same atom or different atoms.

[0038] The "substituents" are not particularly limited as long as they are chemically permissible and have the effect of the present invention. Specific examples of groups which can be "substituents" include the following groups.

[0039] C1-6 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl groups; C2-6 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group (allyl group), propen-2-yl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, and 2-methyl-2-propenyl group; C2-6 alkynyl groups such as an ethynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group), a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, or a 1-methyl-2-propynyl group;

[0040] C3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cubanyl; C6-10 aryl groups such as phenyl and naphthyl groups; C6-10 aryl C1-6 alkyl groups such as benzyl and phenethyl groups; 3- to 6-membered heterocyclyl groups; 3-6 membered heterocyclyl C1-6 alkyl group;

[0041] oxo group; Hydroxyl; C1-6 alkoxy groups, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, or a t-butoxy group; C2-6 alkenyloxy groups, such as a vinyloxy group, an allyloxy group, a 1-propenyloxy group, a propen-2-yloxy group, a 3-butenyloxy group, or a 2-butenyloxy group; C2-6 alkynyloxy groups such as ethynyloxy groups and propargyloxy groups; C6-10 aryloxy groups such as phenoxy and naphthoxy groups; C6-10 aryl C1-6 alkoxy groups such as benzyloxy groups and phenethyloxy groups; 5- to 6-membered heteroaryloxy groups such as thiazolyloxy groups and pyridyloxy groups; 5-6-membered heteroaryl C1-6 alkyloxy groups such as thiazolylmethyloxy groups and pyridylmethyloxy groups;

[0042] Formyl group; C1-6 alkylcarbonyl groups such as acetyl and propionyl groups; Formyloxy group; C1-6 alkylcarbonyloxy groups such as acetyloxy and propionyloxy; C6-10 arylcarbonyl groups such as benzoyl groups; C1-6 alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, or a t-butoxycarbonyl group; C1-6 alkoxycarbonyloxy groups, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, or a t-butoxycarbonyloxy group;

[0043] halogeno groups such as fluoro, chloro, bromo, and iodo groups; C1-6 haloalkyl groups such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a perfluoropropyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, a perfluoroisopropyl group, a 4-fluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a chloromethyl group, a bromomethyl group, a dichloromethyl group, a dibromomethyl group, a trichloromethyl group, a tribromomethyl group, a 1-chloroethyl group, a 2,2,2-trichloroethyl group, a 4-chlorobutyl group, a perchlorohexyl group, and a 2,4,6-trichlorohexyl group; C2-6 haloalkenyl groups, such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group; C2-6 haloalkynyl groups such as a 4,4-dichloro-1-butynyl group, a 4-fluoro-1-pentynyl group, or a 5-bromo-2-pentynyl group; C1-6 haloalkoxy groups such as a trifluoromethoxy group, a 2-chloro-n-propoxy group, or a 2,3-dichlorobutoxy group; C2-6 haloalkenyloxy groups, such as a 2-chloropropenyloxy group or a 3-bromobutenyloxy group; C1-6 haloalkylcarbonyl groups such as a chloroacetyl group, a trifluoroacetyl group, or a trichloroacetyl group;

[0044] Amino group; a mono- or di-C1-6 alkyl-substituted amino group, such as a methylamino group, a dimethylamino group, or a diethylamino group (in the latter case, the C1-6 alkyls may be the same or different); C6-10 arylamino groups such as anilino group and naphthylamino group; C6-10 aryl C1-6 alkylamino groups such as benzylamino groups and phenethylamino groups; Formylamino group; C1-6 alkylcarbonylamino groups, such as an acetylamino group, a propanoylamino group, a butyrylamino group, or an i-propylcarbonylamino group; C1-6 alkoxycarbonylamino groups, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, or an i-propoxycarbonylamino group; C1-6 alkylsulfoximino groups such as S,S-dimethylsulfoximino groups; Unsubstituted or substituted aminocarbonyl groups, such as an aminocarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group, or an N-phenyl-N-methylaminocarbonyl group; imino C1-6 alkyl groups such as an iminomethyl group, a 1-iminoethyl group, and a 1-imino-n-propyl group; substituted or unsubstituted N-hydroxyimino C1-6 alkyl groups, such as an N-hydroxy-iminomethyl group, a 1-(N-hydroxyimino)ethyl group, a 1-(N-hydroxyimino)propyl group, an N-methoxyiminomethyl group, or a 1-(N-methoxyimino)ethyl group; Hydroxyimino group; C1-6 alkoxyimino groups, such as a methoxyimino group, an ethoxyimino group, an n-propoxyimino group, an i-propoxyimino group, or an n-butoxyimino group; Aminocarbonyloxy group; a mono-C1-6 alkyl-substituted aminocarbonyloxy group or a di-C1-6 alkyl-substituted aminocarbonyloxy group such as an ethylaminocarbonyloxy group or a dimethylaminocarbonyloxy group (in the latter case, the C1-6 alkyls may be the same or different);

[0045] Thioxo group; Thiol (mercapto) groups; C1-6 alkylthio groups, such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, an s-butylthio group, or a t-butylthio group; C1-6 haloalkylthio groups, such as a trifluoromethylthio group and a 2,2,2-trifluoroethylthio group; C6-10 arylthio groups, such as a phenylthio group and a naphthylthio group; 5- to 6-membered heteroarylthio groups, such as thiazolylthio groups and pyridylthio groups;

[0046] C1-6 alkylsulfinyl groups such as a methylsulfinyl group, an ethylsulfinyl group, or a t-butylsulfinyl group; C1-6 haloalkylsulfinyl groups such as a trifluoromethylsulfinyl group and a 2,2,2-trifluoroethylsulfinyl group; C6-10 arylsulfinyl groups, such as phenylsulfinyl groups; 5- to 6-membered heteroarylsulfinyl groups such as thiazolylsulfinyl groups and pyridylsulfinyl groups;

[0047] C1-6 alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, or a t-butylsulfonyl group; C1-6 haloalkylsulfonyl groups such as a trifluoromethylsulfonyl group or a 2,2,2-trifluoroethylsulfonyl group; C6-10 arylsulfonyl groups, such as phenylsulfonyl groups; 5- to 6-membered heteroarylsulfonyl groups, such as thiazolylsulfonyl groups and pyridylsulfonyl groups; Sulfo group; C1-6 alkylsulfonyloxy groups, such as a methylsulfonyloxy group, an ethylsulfonyloxy group, or a t-butylsulfonyloxy group; C1-6 haloalkylsulfonyloxy groups such as a trifluoromethylsulfonyloxy group or a 2,2,2-trifluoroethylsulfonyloxy group;

[0048] Tri-C1-6 alkyl-substituted silyl groups, such as trimethylsilyl group, triethylsilyl group, and t-butyldimethylsilyl group; Tri-C6-10 aryl-substituted silyl groups, such as triphenylsilyl groups; C2-C6 alkenyl C1-C6 dialkyl-substituted silyl groups such as an allyldimethylsilyl group and a vinyldimethylsilyl group; C1-C6 alkyldiC6-C10 aryl-substituted silyl groups such as t-butyldiphenylsilyl group and diphenylmethylsilyl group; Di C1-C6 alkyl C6-C10 aryl substituted silyl groups such as dimethylphenylsilyl groups; (C6-C10 phenylC1-C6 alkyl)diC1-C6 alkylsilyl groups such as a benzyldimethylsilyl group and a 3-phenylpropyldimethylsilyl group; C1-C6 alkyl, C6-C10 aryl, C2-C6 alkenylsilyl groups such as methylphenylvinylsilyl groups; Tri-C1-C6 alkoxy-substituted silyl groups, such as a trimethoxysilyl group and a triethoxysilyl group; Di-C1 to C6 alkyl-substituted silyl groups such as dimethylsilyl and diethylsilyl groups; Di-C1-C6 alkoxy-substituted silyl groups, such as dimethoxysilyl group and diethoxysilyl group; C1-C6 alkoxydi-C1-C6 alkyl-substituted silyl groups such as methoxydimethylsilyl groups; C1-C6 alkoxydiC6-C10 aryl-substituted silyl groups such as t-butoxydiphenylsilyl groups; C1-C6 alkyldiC1-C6 alkoxy-substituted silyl groups such as methyldimethoxysilyl group; Cyano group; Nitro group.

[0049] The above "3- to 6-membered heterocyclyl group" includes 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms as ring-constituting atoms. The heterocyclyl group may be either a monocyclic or polycyclic ring. As for the polycyclic heterocyclyl group, as long as at least one ring is a heterocyclic ring, the remaining rings may be any of saturated alicyclic, unsaturated alicyclic, and aromatic hydrocarbon rings. Examples of the "3- to 6-membered heterocyclyl group" include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.

[0050] Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuryl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, and a dioxanyl group.

[0051] Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, a tetrazolyl group, an indonyl group, an isoindolinyl group, an indolizinyl group, a benzimidazolyl group, and a carbazolyl group. Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a cinnolinyl group, a quinazolyl group, a phthalazinyl group, an acridinyl group, a naphthazinyl group, and a phenazinyl group. Examples of the 5- to 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a pyrazolinyl group. Examples of the 3- to 6-membered heterocyclyl1-6 alkyl group include a glycidyl group, a 2-tetrahydrofurylmethyl group, a 2-pyrrolylmethyl group, a 2-imidazolylmethyl group, a 3-isoxazolylmethyl group, a 5-isoxazolylmethyl group, a 2-pyridylmethyl group, a 4-pyridylmethyl group, and a 3-isoxazolinylmethyl group.

[0052] Terms such as "C1-6" indicate that the number of carbon atoms in the core group is 1-6. This number of carbon atoms does not include the number of carbon atoms in the substituent. For example, an ethoxybutyl group is classified as a C2 alkoxyC4 alkyl group because the core group is a butyl group and the substituent is an ethoxy group. However, when the terms "C1-6 alkylcarbonyl" and "C6-10 arylcarbonyl" are used, the number of carbon atoms does not include the carbon of the carbonyl group.

[0053] In these "substituents", any hydrogen atom may be substituted with a group of a different structure.

[0054] In the formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 20 The above substituents include carboxyl groups (COOH) and carboxylate groups (COO - ) is excluded. This means that, for example, 1 is an alkyl group, carboxyalkyl groups are not included in the substituted alkyl groups. 10 and R 11 but not simultaneously a methyl group.

[0055] The carboxylate ion represented by formula (I) is not particularly limited as long as it satisfies the conditions of the chemical formula represented by formula (I). 1 , R 2 and R 20 The substitution position and the like of can be selected arbitrarily, but among them, a carboxylate ion represented by the following formula (V) is preferable. [ka] In formula (V), R 1 , R 2 , R 10 , R 11 , n and m have the same meanings as in formula (I). Specific examples of the carboxylate ion represented by formula (V) include compounds represented by the following formulas.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] The metal organic framework of the present invention can contain an organic ligand other than the carboxylate ion represented by formula (I). Examples of such organic ligands include terephthalic acid, phthalic acid, isophthalic acid, 5-cyanoisophthalic acid, 1,3,5-trimesic acid, 1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-dicarboxybiphenyl, 3,5-dicarboxypyridine, 2,3-dicarboxypyrazine, 1,3,5-tris(4-carboxyphenyl)benzene, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 9,10-anthracenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, [1,1':4',1"]terphenyl-3,3",5,5"-tetracarboxylic acid, biphenyl-3,3",5,5"-tetracarboxylic acid, 3,3',5,5'-tetracarboxamide, 1,2,4,5'-tetrakis(4-carboxyphenyl)benzene ... carboxydiphenylmethane, 1,3,5-tris(4'-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)triazine, 1,2-bis(4-carboxy-3-nitrophenyl)ethene, 1,2-bis(4-carboxy-3-aminophenyl)ethene, trans,trans-muconic acid, fumaric acid, benzimidazole, imidazole, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyrazine, 4,4'-dipyridyl, 1,2-di(4-pyridyl)ethylene, 2,7-diazapyrene, 4,4'-azobispyridine, bis(3-(4-pyridyl)-2,4-pentanedionato)copper, and the like.

[0062] The mixing molar ratio when using the carboxylate ion represented by formula (I) and an organic ligand other than the carboxylate ion represented by formula (I) is not particularly limited. For example, when using an organic ligand other than the carboxylate ion represented by formula (I) as a pillar molecule and constructing a three-dimensional structure such as a pillared layer type by crosslinking with the pillar molecule, it is preferable to use an excess of the organic ligand other than the carboxylate ion represented by formula (I) relative to the carboxylate ion represented by formula (I).

[0063] The method for producing the metal organic framework of the present invention is not particularly limited, and any of the following methods can be used: solution methods such as a solvent diffusion method, a solvent stirring method, and a hydrothermal method; a microwave method in which a reaction solution is irradiated with microwaves to uniformly heat the entire system in a short time; an ultrasonic method in which pressure changes repeatedly occur in a reaction vessel by irradiating a reaction vessel with ultrasound, and this pressure change causes a phenomenon called cavitation in which the solvent forms bubbles and collapses, and at that time, a high-energy field of about 5000 K and 10000 bar is locally formed as a reaction field for each generation of crystals; a solid-phase synthesis method in which a metal ion source and an organic ligand are mixed without using a solvent; and a LAG (liquid assisted grinding) method in which a metal ion source and an organic ligand are mixed by adding water of about the amount of water of crystallization.

[0064] For example, the method includes steps of preparing a first solution containing a metal compound serving as a source of metal ions and a solvent, a second solution containing a carboxylic acid which is a carboxylate ion represented by formula (I) or a precursor thereof and a solvent, and a third solution containing a compound which will become another multidentate ligand and a solvent, as necessary, and a step of mixing the first solution, the second solution, and the third solution to prepare a reaction liquid, and heating the reaction liquid to obtain a metal organic framework. The first to third solutions do not need to be prepared separately, and for example, the metal compound, the carboxylic acid which is a precursor thereof represented by formula (I), the compound which will become another multidentate ligand, and the solvent may be mixed at once to prepare one solution.

[0065] The mixing molar ratio of the metal compound to the carboxylate ion represented by formula (I) or a carboxylic acid that is a precursor thereof can be arbitrarily selected depending on the pore size and surface properties of the resulting metal organic framework, but it is preferable to use 1 mole or more of the metal compound per mole of the carboxylate ion represented by formula (I) or a carboxylic acid that is a precursor thereof, and more preferably 1.1 moles or more, more preferably 1.2 moles or more, more preferably 1.5 moles or more, more preferably 2 moles or more, and even more preferably 3 moles or more.

[0066] The concentration of the metal ions in the reaction solution is preferably in the range of 25 to 200 mol / L. The concentration of the carboxylate ion represented by formula (I) or the carboxylic acid which is a precursor thereof in the reaction liquid is preferably in the range of 10 to 100 mol / L. The concentration of the carboxylate ion represented by formula (I) or the organic ligand other than carboxylate, which is a precursor thereof, in the reaction solution is preferably 25 to 100 mol / L.

[0067] The solvent to be used is not particularly limited, but may be one or more selected from the group consisting of N,N-dimethylformamide (hereinafter sometimes referred to as "DMF"), N,N-diethylformamide (hereinafter sometimes referred to as "DEF"), N,N-dimethylacetamide (hereinafter sometimes referred to as "DMA") and water. Among these, it is preferable to use DMF, DEF or DMA alone, or a DMF / water mixed solvent, a DEF / water mixed solvent or a DMA / water mixed solvent.

[0068] The heating temperature of the reaction solution is not particularly limited, but is preferably in the range of room temperature to 140°C.

[0069] The metal organic framework of the present invention can store gases such as hydrogen, methane, acetylene, carbon dioxide, and nitrogen by adsorbing or occluding the gases. The method for storing gas using the metal organic framework of the present invention is not particularly limited, but a method of contacting the metal organic framework of the present invention with a gas is preferred, and the contact method is not particularly limited. For example, a method of filling a tank with the metal organic framework of the present invention to form a gas storage tank and flowing a gas into the tank, a method of supporting the metal organic framework of the present invention on the surface constituting the inner wall of a tank to form a gas storage tank and flowing a gas into the tank, a method of forming a tank from a material containing the metal organic framework of the present invention to form a gas storage tank and flowing a gas into the tank, etc. can be mentioned. EXAMPLES

[0070] The present invention will be described in detail below using examples, but the present invention is not limited to the scope of the examples. As the carboxylic acid which serves as the precursor of the carboxylate ion represented by formula (I) constituting the metal organic framework of the present invention, organic ligands 1 to 19 shown in Table 1 below were used.

[0071] [Table 1] TIFF0007633229000018.tif236144

[0072] [Production Example 1] Synthesis of organic ligand 1 A solution of 1,4-dibromo-2,5-diethylbenzene (2.5 mmol), 4-methoxycarbonylphenylboronic acid (7.5 mmol), tetrakis(triphenylphosphine)palladium(0) (0.25 mmol), cesium fluoride (1.25 mmol), cesium carbonate (7.5 mmol), 1,4-dioxane (25 mL), and water (1 mL) was heated overnight at 100°C under nitrogen. The reaction solution was returned to room temperature, water was added, and the mixture was separated. The organic layer extracted with dichloromethane was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting solid was purified using silica gel column chromatography (chloroform) to obtain 2.1 mmol of dimethyl 2',5'-diethyl[1,1':4',1''-terphenyl]-4,4''-dicarboxylate as a colorless solid. A solution of 2.0 mmol of the obtained dimethyl 2',5'-diethyl[1,1':4',1''-terphenyl]-4,4''-dicarboxylate, potassium hydroxide (20 mmol), 20 mL of tetrahydrofuran, and 10 mL of water was heated under reflux for 2 days. The reaction solution was returned to room temperature, and after distilling off the tetrahydrofuran, concentrated hydrochloric acid was added. The precipitated solid was filtered and washed with water, and the obtained solid was dried at 100°C to obtain 2.0 mmol of 2',5'-diethyl[1,1':4',1''-terphenyl]-4,4''-dicarboxylate as a colorless solid.

[0073] [Production Example 2] to [Production Example 13] The same procedure as in Production Example 1 was carried out except that the reagents shown in Table 2 below were used instead of 1,4-dibromo-2,5-diethylbenzene, and organic ligands 2 to 13 were all obtained as colorless solids.

[0074] [Table 2]

[0075] [Production Example 14] The same procedure as in Production Example 1 was repeated except that 1,4-dibromo-2,5-dimethoxybenzene was used instead of 1,4-dibromo-2,5-diethylbenzene and 3-hydroxy-4-ethoxycarbonylphenylboronic acid was used instead of 4-methoxycarbonylphenylboronic acid, to obtain organic ligand 14 as a colorless solid.

[0076] [Production Example 15] The diethyl 3,3″-dihydroxy-2′,5′-dimethoxy-[1,1′:4′,1″-terphenyl]-4,4″-dicarboxylate (1.0 mmol) synthesized in Production Example 14, potassium carbonate (3.0 mmol), and methyl iodide (4.0 mmol) were dissolved in 10 mL of DMF and stirred at 100° C. overnight. The reaction solution was returned to room temperature, water was added, and the organic layer extracted with ethyl acetate was dried over magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The obtained solid was separated and purified by silica gel column chromatography (chloroform) to obtain diethyl 2′,3,3″,5′-tetramethoxy-[1,1′:4′,1″-terphenyl]-4,4″-dicarboxylate as a colorless solid. Potassium hydroxide (10.0 mmol), 20 mL of ethanol, and 10 mL of water were added to the obtained colorless solid, and the mixture was stirred at 90° C. overnight. The mixture was cooled to room temperature, dilute hydrochloric acid was added, and the precipitated solid was filtered, washed thoroughly with water, and dried to obtain organic ligand 15, 2',3,3",5'-tetramethoxy-[1,1':4',1"-terphenyl]-4,4"-dicarboxylic acid, as a colorless solid.

[0077] [Production Example 16] Organic ligand 16 was obtained as a colorless solid in the same manner as in Production Example 15, except that propyl iodide was used instead of methyl iodide.

[0078] [Production Example 17]~[Production Example 19] The same procedure as in Production Example 14 was carried out except that the reagents shown in Table 3 below were used, and organic ligands 17 to 19 were obtained as colorless solids.

[0079] [Table 3]

[0080] [Example 1-1] A solution of organic ligand 1 (0.3 mmol), zinc nitrate hexahydrate (0.6 mmol), and 6 mL of DMF was heated in an oven (reaction conditions: 120°C, 24 hours). The reaction solution was returned to room temperature, and the supernatant was removed. The residue was washed with 10 mL of DMF, after which the solvent was removed, and 10 mL of chloroform was added to the residue, followed by immersion overnight. The solid obtained by removing chloroform from the residue immersion solution was vacuum dried at 150°C for 5 hours, yielding metal-organic framework 1-1 as a colorless solid.

[0081] [Examples 1-2] to [Examples 1-16] Metal organic frameworks 1-2 to 1-16 were obtained by the same operation as in Example 1-1, except that the organic ligands and solvents shown in the following Table 4 were used and the reaction was carried out under the reaction conditions shown in Table 4. The results are shown in Table 4.

[0082] [Table 4]

[0083] [Example 2-1] A solution of organic ligand 1 (0.375 mmol), zinc nitrate hexahydrate (0.375 mmol), 1,4-diazabicyclo[2.2.2]octane (0.20 mmol) as an auxiliary ligand, and 7.5 mL of DMF as a solvent was stirred for 15 minutes and then irradiated with ultrasonic waves. The mixture was filtered and the resulting solution was heated in an oven (reaction conditions: 120 ° C, 48 hours). The reaction solution was returned to room temperature, and the precipitated solid was washed three times with 10 mL of DMF, and then washed three more times with 10 mL of chloroform. The obtained solid was immersed in 10 mL of chloroform overnight, and the solid obtained by pressure filtration was vacuum dried at 150 ° C for 5 hours to obtain metal-organic framework 2-1 as colorless crystals.

[0084] [Example 2-2] The same operation as in Example 2-1 was performed except that the organic ligand 2 was used instead of the organic ligand 1, to obtain a metal-organic framework 2-2 as a milky green solid.

[0085] [Example 3-1] Organic ligand 1 (0.5 mmol) was dissolved in 7 mL of DMF, triethylamine (2.0 mmol) was added thereto, and then a solution of zinc acetate dihydrate (1.27 mmol) in 8 mL of DMF was added dropwise. The resulting solution was stirred at room temperature for 20 hours and allowed to stand. The reaction solution was centrifuged, the supernatant was removed, and the resulting solid was immersed in 20 mL of DMF overnight. The supernatant of the solid immersion solution was then removed, and the resulting solid was immersed in 20 mL of chloroform overnight, after which the solid was separated. This operation was repeated three times. The separated solid was then vacuum dried at 150°C for 5 hours to obtain metal-organic framework 3-1 as a light gray powder.

[0086] [Example 3-2] to [Example 3-11] Metal organic frameworks 3-2 to 3-11 were obtained by the same operation as in Example 3-1, except that the organic ligands shown in the following Table 5 were used and the reaction was performed under the reaction conditions shown in Table 5. The results are shown in Table 5.

[0087] [Table 5]

[0088] [Example 4-1] 0.5 mL of triethylamine was added dropwise to a 10 mL DMF solution of organic ligand 1 (0.3 mmol) and zinc nitrate hexahydrate (0.4 mmol) under stirring, and the mixture was stirred at room temperature for 5 minutes. After centrifuging the reaction mixture, the supernatant was removed, 10 mL of DMF was added to the residue, and the mixture was centrifuged again for 10 minutes to remove the supernatant. The residue was immersed in DMF overnight, centrifuged for 10 minutes, the supernatant was removed, and 10 mL of chloroform was added to the residue. The residue immersion solution was further centrifuged to obtain a solid, which was then immersed in 20 mL of chloroform overnight and centrifuged three times. The solid obtained by centrifugation was then vacuum dried at 150 ° C for 5 hours to obtain metal-organic framework 4-1 as a light gray powder.

[0089] [Example 4-2] Metal-organic framework 4-2 was obtained as a colorless powder in the same manner as in Example 4-1, except that organic ligand 2 was used instead of organic ligand 1.

[0090] [Example 4-3] to [Example 4-8] Metal organic frameworks 4-3 to 4-8 were obtained by the same operation as in Example 4-1, except that the organic ligands shown in the following Table 6 were used and the reaction was carried out under the reaction conditions shown in Table 6. The results are shown in Table 6.

[0091] [Table 6]

[0092] [Example 5-1] A solution of organic ligand 1 (0.2 mmol), copper nitrate trihydrate (0.2 mmol), and 4 mL of DMF was irradiated with ultrasonic waves for 15 minutes. The solution was filtered and the obtained solution was heated at 120 ° C for 25 hours. After the reaction solution was returned to room temperature, it was centrifuged for 10 minutes, the supernatant was removed, 10 mL of DMF was added to the residue, and it was centrifuged again for 10 minutes to remove the supernatant. The residue was immersed in DMF overnight, centrifuged for 10 minutes, and DMF was removed by pressure filtration, and 10 mL of chloroform was added to the obtained solid. The solid immersion solution was further centrifuged, and the obtained solid was immersed in 20 mL of chloroform overnight and centrifuged three times. After that, the solid obtained by pressure filtration was vacuum dried at 150 ° C for 5 hours to obtain metal organic framework 5-1.

[0093] [Example 5-2] to [Example 5-7] Metal organic frameworks 5-2 to 5-7 were obtained by the same operation as in Example 5-1, except that the organic ligands shown in the following Table 7 were used and the reaction was performed under the reaction conditions shown in Table 7. The results are shown in Table 7.

[0094] [Table 7]

[0095] [Example 6-1] A solution of organic ligand 1 (0.4 mmol), nickel nitrate hexahydrate (0.8 mmol), 9 mL of THF, and 1 mL of water was heated at 100°C for 48 hours. After the reaction solution was returned to room temperature, the supernatant was removed, DMF was added to the residue, and the supernatant was removed again. Chloroform was then added to the residue, and the residue was immersed overnight. The solid obtained by pressure filtering the immersion liquid was vacuum dried at 150°C for 5 hours to obtain metal-organic framework 6-1 as a yellowish brown powder.

[0096] [Example 6-2] Except for using the organic ligand 2 instead of the organic ligand 1, the same operation as in Example 6-1 was performed to obtain a metal organic framework 6-2 (light green powder).

[0097] [Example 6-3] Except for using the organic ligand 4 instead of the organic ligand 1, the same operation as in Example 6-1 was performed to obtain a metal organic framework 6-3 (light green powder).

[0098] [Example 7-1] A solution of organic ligand 1 (0.3 mmol), zirconium chloride (0.3 mmol), water (3.6 mmol), acetic acid (9 mmol), and 4 mL of DMF was irradiated with ultrasonic waves. The solution was then heated at 120°C for 24 hours. After the reaction solution was returned to room temperature, it was centrifuged for 10 minutes and the supernatant was removed. DMF was added to the residue, centrifuged again for 10 minutes, and the supernatant was removed. The residue was immersed in DMF overnight, and then centrifuged for 10 minutes and the DMF was removed. 10 mL of acetone was added to the residue, and the operation of centrifuging and removing the supernatant was repeated three times, acetone was added again, the mixture was immersed overnight, and then centrifuged. The obtained solid was vacuum dried at 150°C for 5 hours to obtain metal organic framework 7-1 as a colorless solid.

[0099] [Example 7-2] to [Example 7-3] Metal organic frameworks 7-2 to 7-3 were obtained by the same operation as in Example 7-1, except that the reaction was carried out using the organic ligands shown in Table 8 below. The results are shown in Table 8.

[0100] [Table 8]

[0101] [Example 7-4] Zirconium chloride, water, and acetic acid were dissolved in DMF, and the solution was subjected to ultrasonic waves and left to stand at room temperature for 2 days. After that, organic ligand 3 was added, and the same treatment as in Example 7-1 was carried out to obtain metal organic framework 7-4 (colorless powder).

[0102] [Example 7-5] The same operation as in Example 7-4 was carried out except that water was not added, thereby obtaining metal organic framework 7-5 (colorless powder).

[0103] [Example 7-6] to [Example 7-25] Metal organic frameworks 7-6 to 7-25 were obtained by the same operation as in Example 7-1, except that the reaction was carried out using the organic ligands shown in Table 9 below. The results are shown in Table 9.

[0104] [Table 9]

[0105] [Example 8-1] A solution of organic ligand 1 (0.175 mmol), zirconium oxide chloride octahydrate (0.175 mmol), and 4 mL of a mixed solvent of formic acid:DMF=1:7 was irradiated with ultrasonic waves. The solution was then heated at 120°C for 24 hours. The reaction solution was returned to room temperature, and the supernatant was removed. DMF was added to the residue, centrifuged again for 10 minutes, and the operation of removing the supernatant was repeated three times, after which DMF was added and the solution was immersed overnight. After removing DMF from the residue immersion solution, methanol was added to the residue, and the operation of centrifuging and removing the supernatant was repeated three times. Methanol was added to the residue again, and the solution was immersed overnight, after which methanol was removed, and the obtained solid was vacuum dried at 150°C for 5 hours to obtain metal organic framework 8-1 as a light gray powder.

[0106] [Example 9-1] Organic ligand 2 (0.36 mmol), tetraisopropyl orthotitanate (0.074 mmol), 2.2 g acetic acid, and 7 mL DMF were mixed and sonicated. The mixture was then heated at 120°C for 48 hours. After returning to room temperature, the mixture was centrifuged for 10 minutes and the supernatant was removed. DMF was added to the residue, centrifuged again for 10 minutes, and the supernatant was removed. After immersion in DMF overnight, the mixture was centrifuged for 10 minutes and the DMF was removed. After that, 10 mL of acetone was added, and the centrifugation and supernatant removal were repeated three times. Acetone was added again and the mixture was immersed overnight. The centrifuged solid was vacuum dried at 150°C for 5 hours to obtain metal-organic framework 9-1 as an off-white powder.

[0107] [Example 9-2] to [Example 9-6] Metal organic frameworks 9-2 to 9-6 were obtained by the same operation as in Example 9-1, except that the reaction was carried out using the organic ligands shown in Table 10 below. The results are shown in Table 10.

[0108] [Table 10]

[0109] [Example 10-1] 5 mL of DMF was added to organic ligand 2 (0.5 mmol) and chromium chloride hexahydrate (0.5 mmol), and the mixture was subjected to ultrasonic waves. The solution was heated at 190°C for 24 hours. After returning to room temperature, the mixture was centrifuged for 10 minutes, and the supernatant was removed. 10 mL of DMF was added to the residue, and the mixture was centrifuged again for 10 minutes, and the supernatant was removed. After immersion in DMF overnight, the mixture was centrifuged for 10 minutes, and the DMF was removed by pressure filtration, and 10 mL of chloroform was added. The centrifuged solid was immersed in 20 mL of chloroform overnight and centrifuged again, and this washing operation was repeated three times. The solid obtained by pressure filtration was then vacuum dried at 150°C for 5 hours to obtain metal-organic framework 10-1 as a green solid.

[0110] [Example 10-2] to [Example 10-4] Metal organic frameworks 10-2 to 10-4 were obtained by the same operation as in Example 10-1, except that the reaction was carried out using the organic ligands shown in Table 11 below. The results are shown in Table 11.

[0111] [Table 11]

[0112] [Example 11-1] 5 mL of DMF was added to organic ligand 2 (0.18 mmol) and aluminum nitrate nonahydrate (0.24 mmol), and the mixture was subjected to ultrasonic waves. The solution was heated at 120°C for 24 hours. After returning to room temperature, the mixture was centrifuged for 10 minutes, and the supernatant was removed. 10 mL of DMF was added to the residue, and the mixture was centrifuged again for 10 minutes, and the supernatant was removed. After immersion in DMF overnight, the mixture was centrifuged for 10 minutes, and the DMF was removed by pressure filtration, and 10 mL of acetone was added. The centrifuged solid was immersed in 20 mL of acetone overnight and centrifuged again, and this washing operation was repeated three times. The solid obtained by pressure filtration was then vacuum dried at 150°C for 5 hours to obtain metal-organic framework 11-1 as a colorless powder.

[0113] [Examples 11-2] to [Examples 11-14] Metal organic frameworks 11-2 to 11-14 were obtained by the same operation as in Example 11-1, except that the reaction was carried out using the organic ligands shown in Table 12 below. The results are shown in Table 12.

[0114] [Table 12]

[0115] [Example 12-1] Organic ligand 8 (0.1 mmol) and iron (III) chloride (0.25 mmol) were added with 8 mL of DMF and 1 mL of acetic acid, and then sonicated. The solution was heated at 150°C for 168 hours. After returning to room temperature, the mixture was centrifuged for 10 minutes and the supernatant was removed. 10 mL of DMF was added to the residue, and the mixture was centrifuged again for 10 minutes and the supernatant was removed. After immersion in DMF overnight, the mixture was centrifuged for 10 minutes and filtered under pressure to remove the DMF, and then 10 mL of chloroform was added. The centrifuged solid was immersed in 20 mL of chloroform overnight and centrifuged again, and this washing operation was repeated three times. The solid obtained by pressure filtration was then vacuum dried at 150°C for 5 hours to obtain metal-organic framework 12-1 as a brown powder.

[0116] [Example 12-2] to [Example 12-4] Metal organic frameworks 12-2 to 12-4 were obtained by the same operation as in Example 12-1, except that the reaction was carried out using the organic ligands shown in Table 13 below. The results are shown in Table 13.

[0117] [Table 13]

[0118] [BET specific surface area measurement and hydrogen storage capacity measurement] For some of the obtained metal-organic frameworks, the BET specific surface area and the hydrogen storage capacity at 77 K under atmospheric pressure were measured. The BET specific surface area and the hydrogen storage capacity at 77K under atmospheric pressure were measured using a gas adsorption measurement device Tristar-II (Micromeritics). The BET specific surface area was calculated by the following method. Approximately 50 mg of the metal-organic framework was placed inside a glass cell. The inside of the glass cell was depressurized to a vacuum at a temperature of 135°C and dried for 6 hours. The glass cell was attached to a gas adsorption measurement device and immersed in a thermostatic bath containing liquid nitrogen. The pressure of the nitrogen contained in the glass cell was gradually increased. When the pressure of the nitrogen introduced into the glass cell reached 1.0×10 5 The measurement was continued until the pressure reached 1 Pa.

[0119] The amount of hydrogen stored at 77K and normal pressure was calculated as follows. After measuring nitrogen, the gas type was changed to hydrogen and measurements were performed. The pressure of hydrogen contained in the glass cell was gradually increased. When the pressure of hydrogen introduced into the glass cell was 1.0×10 5 The measurement was continued until the pressure reached 1 Pa. The measured BET specific surface area and the measured hydrogen storage capacity at 77 K and atmospheric pressure are shown in Table 14. In the table, "-" means that the measurement was not performed.

[0120] [Table 14] TIFF0007633229000032.tif219168TIFF0007633229000033.tif103167

[0121] [Single crystal X-ray structure analysis] The metal organic frameworks 1-2 and 2-2 obtained in Examples 1-2 and 2-2 were subjected to X-ray structural analysis under the measurement conditions shown below. [Measurement conditions] A single grain of colorless and transparent single crystal of the metal-organic framework 1-2 obtained in Example 1-2 having a size of 0.1 × 0.05 × 0.05 mm was placed on a micromount, and diffraction data was obtained by irradiating the single crystal with X-rays having a wavelength of 0.78192 Å using a single crystal X-ray analyzer (D8VENTURE, manufactured by Bruker). The diffraction data obtained was analyzed to determine the structure, and the results are shown in Table 15.

[0122] [Table 15]

[0123] The metal organic framework 2-2 obtained in Example 2-2 was subjected to X-ray structural analysis under the same conditions as those of the measurement described above. The results are shown in Table 16.

[0124] [Table 16] [Industrial Applicability]

[0125] The metal organic framework of the present invention can store gases such as hydrogen at a practical level, which will, for example, make it easier to utilize hydrogen as we move towards a hydrogen society.

Claims

1. A metal organic framework comprising a carboxylate ion represented by formula (V) and a polyvalent metal ion bonded thereto. 【Chemistry 1】 In formula (V), R 1 and R 2 each independently represent a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group. n represents the number of R 1 and is 0, 1, 2, 3 or 4, and when n is 2 or more, a plurality of R 1 s may be the same or different. m represents the number of R 2 s and is 0, 1, 2, 3 or 4, and when m is 2 or more, the multiple R 2 s may be the same or different. R 10 and R 11 each independently represent a C2-6 alkyl group, a C3-8 cycloalkyl group, a C1-6 alkoxy group, or a halogeno group.

2. 2. The metal organic structure according to claim 1, wherein the polyvalent metal ion is an ion of at least one metal selected from Zn, Fe, Co, Ni, Cu, Al, Zr, Ti, Cr, and Mg.

3. The metal organic framework according to claim 1 or 2, further comprising an organic ligand other than the carboxylate ion represented by formula (V) as a constituent component.

4. The metal organic framework according to claim 1, which is a hydrogen storage material for storing hydrogen.

5. A gas storage method comprising the steps of contacting a gas with the metal-organic framework according to any one of claims 1 to 4, and adsorbing or occluding the gas inside the metal-organic framework.

6. A method for storing hydrogen gas, comprising the steps of contacting hydrogen gas with the metal organic framework described in claim 4 and adsorbing or occluding the hydrogen gas inside the metal organic framework.

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