JP2024012177A - Metal-organic framework coordinated with carboxylate ion having diphenyl methane skeleton - Google Patents
Metal-organic framework coordinated with carboxylate ion having diphenyl methane skeleton Download PDFInfo
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- JP2024012177A JP2024012177A JP2023115329A JP2023115329A JP2024012177A JP 2024012177 A JP2024012177 A JP 2024012177A JP 2023115329 A JP2023115329 A JP 2023115329A JP 2023115329 A JP2023115329 A JP 2023115329A JP 2024012177 A JP2024012177 A JP 2024012177A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 20
- 125000006840 diphenylmethane group Chemical group 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 127
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000011232 storage material Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 85
- 239000002184 metal Substances 0.000 claims description 85
- 239000007789 gas Substances 0.000 claims description 37
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 44
- 239000013110 organic ligand Substances 0.000 description 280
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 136
- 239000007787 solid Substances 0.000 description 132
- 239000000243 solution Substances 0.000 description 79
- 150000003839 salts Chemical class 0.000 description 77
- 238000004519 manufacturing process Methods 0.000 description 65
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 64
- 238000010438 heat treatment Methods 0.000 description 56
- 239000012528 membrane Substances 0.000 description 43
- 239000001257 hydrogen Substances 0.000 description 42
- 229910052739 hydrogen Inorganic materials 0.000 description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 40
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 39
- -1 carboxylic acid ion Chemical class 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 34
- 239000002904 solvent Substances 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 33
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 21
- 238000001914 filtration Methods 0.000 description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- 125000005647 linker group Chemical group 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 229910007926 ZrCl Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 7
- 229910009112 xH2O Inorganic materials 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 6
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- ROMPPAWVATWIKR-UHFFFAOYSA-N 4-[3-(4-chlorophenyl)-1,2,4-oxadiazol-5-yl]butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2C=CC(Cl)=CC=2)=N1 ROMPPAWVATWIKR-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 2
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910007340 Zn(OAc)2.2H2O Inorganic materials 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002346 iodo group Chemical group I* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000786 liquid-assisted grinding Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 2
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 2
- VCGRFBXVSFAGGA-UHFFFAOYSA-N (1,1-dioxo-1,4-thiazinan-4-yl)-[6-[[3-(4-fluorophenyl)-5-methyl-1,2-oxazol-4-yl]methoxy]pyridin-3-yl]methanone Chemical compound CC=1ON=C(C=2C=CC(F)=CC=2)C=1COC(N=C1)=CC=C1C(=O)N1CCS(=O)(=O)CC1 VCGRFBXVSFAGGA-UHFFFAOYSA-N 0.000 description 1
- TXXHDPDFNKHHGW-UHFFFAOYSA-N (2E,4E)-2,4-hexadienedioic acid Natural products OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VMLKTERJLVWEJJ-UHFFFAOYSA-N 1,5-naphthyridine Chemical compound C1=CC=NC2=CC=CN=C21 VMLKTERJLVWEJJ-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- ZYIMHOWVWWHLDN-UHFFFAOYSA-N 2-(4-bromophenyl)-1,3-dioxolane Chemical compound C1=CC(Br)=CC=C1C1OCCO1 ZYIMHOWVWWHLDN-UHFFFAOYSA-N 0.000 description 1
- GOONVUGWFUNIJB-UHFFFAOYSA-N 2-amino-3,5-dibromobenzohydrazide Chemical compound NNC(=O)C1=CC(Br)=CC(Br)=C1N GOONVUGWFUNIJB-UHFFFAOYSA-N 0.000 description 1
- NYYDJNCUEKKYEX-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C(=O)(O)C1=C(C=C(C=C1)C=CC1=CC(=C(C=C1)C(=O)O)N)N NYYDJNCUEKKYEX-UHFFFAOYSA-N 0.000 description 1
- DQRKTVIJNCVZAX-UHFFFAOYSA-N 4-(2-pyridin-4-ylethyl)pyridine Chemical compound C=1C=NC=CC=1CCC1=CC=NC=C1 DQRKTVIJNCVZAX-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- MGFJDEHFNMWYBD-OWOJBTEDSA-N 4-[(e)-2-pyridin-4-ylethenyl]pyridine Chemical group C=1C=NC=CC=1/C=C/C1=CC=NC=C1 MGFJDEHFNMWYBD-OWOJBTEDSA-N 0.000 description 1
- DWSOSVOJGDWEQY-UHFFFAOYSA-N 4-[1,3-bis(4-carboxyphenyl)-2,4-dihydrotriazin-5-yl]benzoic acid Chemical compound C(=O)(O)C1=CC=C(C=C1)N1NN(CC(=C1)C1=CC=C(C=C1)C(=O)O)C1=CC=C(C=C1)C(=O)O DWSOSVOJGDWEQY-UHFFFAOYSA-N 0.000 description 1
- SRTQKANXPMBQCX-UHFFFAOYSA-N 4-[2,4,5-tris(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=C(C=2C=CC(=CC=2)C(O)=O)C=C1C1=CC=C(C(O)=O)C=C1 SRTQKANXPMBQCX-UHFFFAOYSA-N 0.000 description 1
- JEQOXOTWBCFOQQ-UHFFFAOYSA-N 4-[2-(4-carboxy-3-nitrophenyl)ethenyl]-2-nitrobenzoic acid Chemical compound C1=CC(=C(C=C1C=CC2=CC(=C(C=C2)C(=O)O)[N+](=O)[O-])[N+](=O)[O-])C(=O)O JEQOXOTWBCFOQQ-UHFFFAOYSA-N 0.000 description 1
- PEQRGMPXYDIZSX-UHFFFAOYSA-N 4-[4-[3,5-bis[4-(4-carboxyphenyl)phenyl]phenyl]phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C=2C=C(C=C(C=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=C1 PEQRGMPXYDIZSX-UHFFFAOYSA-N 0.000 description 1
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- YKADUTAIRWMMFI-UHFFFAOYSA-N 5-cyanobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C#N)=CC(C(O)=O)=C1 YKADUTAIRWMMFI-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- ZPIPUFJBRZFYKJ-UHFFFAOYSA-N C1=NC=C2C=CC3=CN=CC4=CC=C1C2=C34 Chemical compound C1=NC=C2C=CC3=CN=CC4=CC=C1C2=C34 ZPIPUFJBRZFYKJ-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910019131 CoBr2 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- HQCSLVYEWMDWIZ-UHFFFAOYSA-N H4TPTC Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=CC(=CC=2)C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 HQCSLVYEWMDWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- AYCPARAPKDAOEN-LJQANCHMSA-N N-[(1S)-2-(dimethylamino)-1-phenylethyl]-6,6-dimethyl-3-[(2-methyl-4-thieno[3,2-d]pyrimidinyl)amino]-1,4-dihydropyrrolo[3,4-c]pyrazole-5-carboxamide Chemical compound C1([C@H](NC(=O)N2C(C=3NN=C(NC=4C=5SC=CC=5N=C(C)N=4)C=3C2)(C)C)CN(C)C)=CC=CC=C1 AYCPARAPKDAOEN-LJQANCHMSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101100131043 Oryza sativa subsp. japonica MOF1 gene Proteins 0.000 description 1
- 101100140586 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) NAM7 gene Proteins 0.000 description 1
- 101100528972 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) RPD3 gene Proteins 0.000 description 1
- 229910018057 ScCl3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910007938 ZrBr4 Inorganic materials 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FDFGHPKPHFUHBP-UHFFFAOYSA-N anthracene-9,10-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=C(C(O)=O)C2=C1 FDFGHPKPHFUHBP-UHFFFAOYSA-N 0.000 description 1
- NLDGILPIGBAYHN-UHFFFAOYSA-N butyl 4-(4-butoxycarbonylphenyl)benzoate Chemical compound C1=CC(C(=O)OCCCC)=CC=C1C1=CC=C(C(=O)OCCCC)C=C1 NLDGILPIGBAYHN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YIHLHMMKAVROOJ-UHFFFAOYSA-N dimethyl 2,5-dimethoxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(OC)=C(C(=O)OC)C=C1OC YIHLHMMKAVROOJ-UHFFFAOYSA-N 0.000 description 1
- XYQCGGPYZALUAE-UHFFFAOYSA-N dimethyl 2,5-dimethylbenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(C)=C(C(=O)OC)C=C1C XYQCGGPYZALUAE-UHFFFAOYSA-N 0.000 description 1
- MPJYZGXACATOPK-UHFFFAOYSA-N dimethyl 2,5-diphenylbenzene-1,4-dicarboxylate Chemical compound COC(=O)C=1C=C(C=2C=CC=CC=2)C(C(=O)OC)=CC=1C1=CC=CC=C1 MPJYZGXACATOPK-UHFFFAOYSA-N 0.000 description 1
- XZWYGKPSIBDYDY-UHFFFAOYSA-N dimethyl 5-methoxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(OC)=CC(C(=O)OC)=C1 XZWYGKPSIBDYDY-UHFFFAOYSA-N 0.000 description 1
- DWLNVWOJNQXRLG-UHFFFAOYSA-N dimethyl 5-methylbenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(C)=CC(C(=O)OC)=C1 DWLNVWOJNQXRLG-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- XUPMSLUFFIXCDA-UHFFFAOYSA-N dipyridin-4-yldiazene Chemical compound C1=NC=CC(N=NC=2C=CN=CC=2)=C1 XUPMSLUFFIXCDA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XGVXKJKTISMIOW-ZDUSSCGKSA-N simurosertib Chemical compound N1N=CC(C=2SC=3C(=O)NC(=NC=3C=2)[C@H]2N3CCC(CC3)C2)=C1C XGVXKJKTISMIOW-ZDUSSCGKSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TXXHDPDFNKHHGW-ZPUQHVIOSA-N trans,trans-muconic acid Chemical compound OC(=O)\C=C\C=C\C(O)=O TXXHDPDFNKHHGW-ZPUQHVIOSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- RGCHNYAILFZUPL-UHFFFAOYSA-N trimethyl benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1 RGCHNYAILFZUPL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
本発明は、ジフェニルメタン骨格を有するカルボン酸イオンと多価金属イオンが結合してなる金属有機構造体、前記金属有機構造体を含むガス貯蔵剤、及び前記金属有機構造体にガスを接触させる工程を含むガスの貯蔵方法に関する。 The present invention provides a metal-organic structure formed by bonding a carboxylic acid ion having a diphenylmethane skeleton with a polyvalent metal ion, a gas storage agent containing the metal-organic structure, and a step of bringing a gas into contact with the metal-organic structure. This invention relates to a method for storing gas containing gas.
金属有機構造体（以下「ＭＯＦ」ということがある。）は、金属イオンとそれらを連結する架橋性の有機配位子を組み合わせることで内部に空間（つまり細孔）を持つ高分子構造を有する固体状の物質であり、ガスの貯蔵や分離などの機能をもつ多孔性材料として、この十数年高い興味が持たれてきた。例えば、メタンテトラ（ｐ－安息香酸）と硝酸銅（II）を、酸性条件下、ジメチルホルムアミドと水の混合溶媒中で加熱することにより、次の分子式（Ａ）のＭＯＦが得られることが報告されている。（式中：Ｌ１は、メタンテトラ（ｐ－安息香酸）のカルボン酸イオンを示す。） A metal-organic framework (hereinafter sometimes referred to as "MOF") has a polymer structure with internal spaces (i.e., pores) created by combining metal ions and crosslinking organic ligands that connect them. It is a solid substance and has attracted great interest over the past decade as a porous material with functions such as gas storage and separation. For example, it has been reported that MOF with the following molecular formula (A) can be obtained by heating methane tetra(p-benzoic acid) and copper(II) nitrate in a mixed solvent of dimethylformamide and water under acidic conditions. has been done. (In the formula: L 1 represents a carboxylic acid ion of methane tetra(p-benzoic acid).)
［式１］
表面積は１５６０ｍ２／ｇで、水素、窒素等のガスを貯蔵できることが知られている（非特許文献１参照）。このような開発が行われるなか、金属有機構造体は、用いる金属種、配位子、反応条件により大きく構造が変化することが知られており、ガス貯蔵機能を有する新規な金属有機構造体の開発が更に求められている。 It has a surface area of 1560 m 2 /g and is known to be able to store gases such as hydrogen and nitrogen (see Non-Patent Document 1). While such development is being carried out, it is known that the structure of metal-organic frameworks changes greatly depending on the metal species, ligands, and reaction conditions used, and new metal-organic frameworks with gas storage functions are being developed. Further development is required.
本発明は、ガス貯蔵機能を有する新規な金属有機構造体並びにそれを用いたガス貯蔵剤及びガス貯蔵方法を提供することを課題とする。 An object of the present invention is to provide a novel metal-organic structure having a gas storage function, a gas storage agent, and a gas storage method using the same.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、ジフェニルメタン骨格を有する特定のカルボン酸を有機配位子として得られる新規な金属有機構造体を見いだした。また、それらの新規な金属有機構造体には、高い水素貯蔵能力があることを見いだし、本発明を完成するに至った。 The present inventors conducted extensive studies to solve the above problems, and as a result, discovered a novel metal organic structure that can be obtained using a specific carboxylic acid having a diphenylmethane skeleton as an organic ligand. Furthermore, the inventors discovered that these novel metal-organic structures have a high hydrogen storage capacity, leading to the completion of the present invention.
すなわち、本発明は以下に示す事項により特定されるものである。
［１］式（１）で表されるカルボン酸イオンと多価金属イオンとが結合してなる金属有機構造体。
That is, the present invention is specified by the matters shown below.
[1] A metal-organic structure formed by bonding a carboxylic acid ion represented by formula (1) with a polyvalent metal ion.
Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
ｎ１、ｎ２、ｎ３及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。
Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。
ｐは、１～３のいずれかの整数である。
Ｌは、単結合又は２～４価の有機基である。）
Each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
n1, n2, n3 and n4 are each independently an integer of 0 to 4.
When X is 2 or more, each X may be the same or different from each other.
p is an integer of 1 to 3.
L is a single bond or a divalent to tetravalent organic group. )
［２］式（１）で表されるカルボン酸イオンが、式（２）で表されるカルボン酸イオンである上記［１］の金属有機構造体。 [2] The metal-organic structure of [1] above, wherein the carboxylic acid ion represented by formula (1) is a carboxylic acid ion represented by formula (2).
Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
ｎ１、ｎ２、ｎ３及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。
Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。
Ｌａは、単結合又は２価の有機基である。）
Each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
n1, n2, n3 and n4 are each independently an integer of 0 to 4.
When X is 2 or more, each X may be the same or different from each other.
L a is a single bond or a divalent organic group. )
［３］多価金属イオンが、元素の周期表の第２族～第１３族の金属からなる群から選ばれる少なくとも１種の金属イオンである上記［１］又は［２］の金属有機構造体。
［４］補助配位子を構成成分として更に含む上記［１］～［３］のいずれかに記載の金属有機構造体。
［５］上記［１］～［４］のいずれかの金属有機構造体を含むガス貯蔵剤。
［６］上記［１］～［４］のいずれかの金属有機構造体にガスを接触させる工程を含むガスの貯蔵方法。
[3] The metal-organic structure according to [1] or [2] above, wherein the polyvalent metal ion is at least one metal ion selected from the group consisting of metals from Groups 2 to 13 of the Periodic Table of the Elements. .
[4] The metal-organic structure according to any one of [1] to [3] above, further comprising an auxiliary ligand as a constituent component.
[5] A gas storage agent containing the metal-organic structure according to any one of [1] to [4] above.
[6] A method for storing a gas, which includes the step of bringing a gas into contact with the metal-organic structure according to any one of [1] to [4] above.
本発明の金属有機構造体は新規であり、水素、窒素等のガスを貯蔵することができる。 The metal-organic framework of the present invention is novel and capable of storing gases such as hydrogen and nitrogen.
本発明の金属有機構造体は、式（１）で表されるカルボン酸イオンと多価金属イオンとが結合してなる金属有機構造体である。 The metal-organic structure of the present invention is a metal-organic structure formed by bonding a carboxylic acid ion represented by formula (1) with a polyvalent metal ion.
式（１）中、Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基、またはハロゲノ基である。Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基、またはハロゲノ基である。ｎ１、ｎ２、ｎ３、及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。ｐは、１～３のいずれかの整数である。Ｌは、単結合又は２～４価の有機基である。 In formula (1), each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group. Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group. n1, n2, n3, and n4 are each independently an integer of 0 to 4. When X is 2 or more, each X may be the same or different from each other. p is an integer of 1 to 3. L is a single bond or a divalent to tetravalent organic group.
ＲのＣ１～６アルキル基としては、直鎖でも、分岐鎖であってもよく、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｉ－プロピル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｉ－ペンチル基、ネオペンチル基、２－メチル－ｎ－ブチル基、ｉ－ヘキシル基等を挙げることができる。ＲのＣ１～６アルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基等を挙げることができる。Ｒのハロゲノ基としては、フルオロ基、クロロ基、ブロモ基、イオド基等を挙げることができる。 The C1-6 alkyl group of R may be linear or branched, and may be a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i- Examples include propyl group, i-butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methyl-n-butyl group, and i-hexyl group. Examples of the C1-6 alkoxy group for R include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, etc. can. Examples of the halogeno group for R include a fluoro group, a chloro group, a bromo group, an iodo group, and the like.
ＸのＣ１～６アルキル基としては、直鎖でも、分岐鎖であってもよく、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｉ－プロピル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｉ－ペンチル基、ネオペンチル基、２－メチル－ｎ－ブチル基、ｉ－ヘキシル基等を挙げることができる。ＸのＣ１～６アルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基等を挙げることができる。Ｘのハロゲノ基としては、フルオロ基、クロロ基、ブロモ基、イオド基等を挙げることができる。本願明細書における「Ｃ１～６」などの用語は、母核となる基の炭素原子数が１～６個などであることを表している。 The C1-6 alkyl group of Examples include propyl group, i-butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methyl-n-butyl group, and i-hexyl group. Examples of the C1-6 alkoxy group of X include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, etc. can. Examples of the halogeno group of X include a fluoro group, a chloro group, a bromo group, an iodo group, and the like. In the present specification, terms such as "C1-6" indicate that the number of carbon atoms in the group serving as a core is 1 to 6.
Ｌの２～４価の有機基としては、例えば、アルカンから誘導される２～４価の連結基、エテンから誘導される２～４価の連結基、アリールから誘導される２～４価の連結基、ヘテロアリールから誘導される２～４価の連結基等を挙げることができる。 Examples of the divalent to tetravalent organic group for L include a divalent to tetravalent linking group derived from an alkane, a divalent to tetravalent linking group derived from ethene, and a divalent to tetravalent linking group derived from aryl. Examples include linking groups, divalent to tetravalent linking groups derived from heteroaryl, and the like.
アルカンから誘導される２～４価の連結基とは、アルカンを母核として、アルカンを構成する炭素上の任意の水素２～４個を結合手に変換したものであり、具体的には、以下に示す連結基を例示することができる。なお、結合手とは、他の官能基と結合を形成することのできる電子が配置されている状態を意味し、炭素上に記載されている「－」は、結合手を表す。 A divalent to tetravalent linking group derived from an alkane is one in which 2 to 4 arbitrary hydrogen atoms on the carbon atoms constituting the alkane are converted into bonds using an alkane as a mother nucleus, and specifically, The following linking groups can be exemplified. Note that a bond means a state in which electrons that can form a bond with another functional group are arranged, and "-" written on a carbon represents a bond.
エテンから誘導される２～４価の連結基とは、エテンを母核として、アルカンを構成する炭素上の任意の水素２～４個を結合手に変換したものであり、具体的には、以下に示す連結基を例示することができる。 A divalent to tetravalent linking group derived from ethene is one in which 2 to 4 arbitrary hydrogen atoms on the carbon atoms constituting an alkane are converted into bonds using ethene as the mother nucleus, and specifically, The following linking groups can be exemplified.
アリールから誘導される２～４価の連結基とは、アリールを母核として、アリールを構成する炭素上の任意の水素２～４個を結合手に変換したものであり、具体的には、以下に示す連結基を例示することができる。 A divalent to tetravalent linking group derived from an aryl is one in which 2 to 4 arbitrary hydrogen atoms on the carbon atoms constituting the aryl are converted into bonds using the aryl as the core, and specifically, The following linking groups can be exemplified.
ヘテロアリールから誘導される２～４価の連結基とは、ヘテロアリールを母核として、ヘテロアリールを構成するヘテロ原子上又は炭素上の任意の水素２～４個を結合手に変換したものであり、具体的には、以下に示す連結基を例示することができる。 A divalent to tetravalent linking group derived from a heteroaryl is one in which 2 to 4 arbitrary hydrogen atoms on the hetero atom or carbon that constitute the heteroaryl are converted into a bond using the heteroaryl as the mother nucleus. Specifically, the following linking groups can be exemplified.
式（１）で表されるカルボン酸イオンとして具体的には、以下の式に表す化合物等を例示することができる。 Specific examples of the carboxylic acid ion represented by formula (1) include compounds represented by the following formula.
本発明の金属有機構造体は、式（２）で表されるカルボン酸イオンと多価金属イオンが結合してなる金属有機構造体であることが好ましい。式（２）で表されるカルボン酸イオンは、式（１）で表されるカルボン酸イオンにおいて、Ｌを単結合又は２価の有機基としたものである。 The metal-organic structure of the present invention is preferably a metal-organic structure formed by bonding a carboxylic acid ion represented by formula (2) with a polyvalent metal ion. The carboxylic acid ion represented by formula (2) is a carboxylic acid ion represented by formula (1) in which L is a single bond or a divalent organic group.
式（２）中、Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。ｎ１、ｎ２、ｎ３及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。Ｌａは、単結合又は２価の有機基である。Ｒ及びＸについては、式（１）の場合と同じである。Ｌａの２価の有機基については、式（１）におけるＬの２価の有機基と同じである。 In formula (2), each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group. Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group. n1, n2, n3 and n4 are each independently an integer of 0 to 4. When X is 2 or more, each X may be the same or different from each other. L a is a single bond or a divalent organic group. R and X are the same as in formula (1). The divalent organic group of L a is the same as the divalent organic group of L in formula (1).
本発明の金属有機構造体における多価金属イオンとしては、２価以上の金属のイオンであれば、特に制限されないが、元素周期表の第２族～第１３族の金属からなる群から選ばれる少なくとも１種の金属のイオンが好ましく、Ｚｎ、Ａｌ、Ｃｕ、Ｚｒ、Ｎｉ、Ｃｏ、Ｃｒ、Ｆｅ、Ｓｃ、Ｍｏ、Ｍｎ、Ｔｉ及びＭｇから選ばれる少なくとも１種の金属のイオンがより好ましい。本発明の金属有機構造体において、式（１）で表されるカルボン酸イオンと結合する多価金属イオンは、１種でもよく２種以上でもよい。 The polyvalent metal ion in the metal-organic structure of the present invention is not particularly limited as long as it is a divalent or higher metal ion, but is selected from the group consisting of metals from Groups 2 to 13 of the Periodic Table of Elements. Ions of at least one metal are preferred, and ions of at least one metal selected from Zn, Al, Cu, Zr, Ni, Co, Cr, Fe, Sc, Mo, Mn, Ti, and Mg are more preferred. In the metal-organic structure of the present invention, the number of polyvalent metal ions bonded to the carboxylic acid ion represented by formula (1) may be one type or two or more types.
これらの多価金属イオンは、種々の塩の形で供給される。金属塩として具体的には、硝酸亜鉛（Ｚｎ（ＮＯ３）２・ｘＨ２Ｏ）、硝酸チタン（Ｔｉ（ＮＯ３）４・ｘＨ２Ｏ）、硝酸コバルト（Ｃｏ（ＮＯ３）２・ｘＨ２Ｏ）、硝酸鉄（III）（Ｆｅ（ＮＯ３）３・ｘＨ２Ｏ）、硝酸鉄（II）（Ｆｅ（ＮＯ３）２・ｘＨ２Ｏ）、硝酸ニッケル（II）（Ｎｉ（ＮＯ３）２・ｘＨ２Ｏ）、硝酸銅（II）（Ｃｕ（ＮＯ３）２・ｘＨ２Ｏ）、硝酸アルミニウム（III）（Ａｌ（ＮＯ３）３・ｘＨ２Ｏ）、硝酸マグネシウム（II）（Ｍｇ（ＮＯ３）２・ｘＨ２Ｏ）；塩化亜鉛（ＺｎＣｌ２・ｘＨ２Ｏ）、塩化チタン（ＴｉＣｌ４・ｘＨ２Ｏ）、塩化ジルコニウム（ＺｒＣｌ４・ｘＨ２Ｏ）、塩化コバルト（ＣｏＣｌ２・ｘＨ２Ｏ）、塩化鉄（III）（ＦｅＣｌ３・ｘＨ２Ｏ）、塩化鉄（II）（ＦｅＣｌ２・ｘＨ２Ｏ）、塩化クロム（III）（ＣｒＣｌ３・ｘＨ２Ｏ）、塩化スカンジウム（III）（ＳｃＣｌ３・ｘＨ２Ｏ）、塩化マンガン（II）（ＭｎＣｌ２・ｘＨ２Ｏ）；酢酸亜鉛（Ｚｎ（ＣＨ３ＣＯＯ）２・ｘＨ２Ｏ）、酢酸チタン（Ｔｉ（ＣＨ３ＣＯＯ）４・ｘＨ２Ｏ）、酢酸ジルコニウム（Ｚｒ（ＣＨ３ＣＯＯ）４・ｘＨ２Ｏ）、酢酸コバルト（Ｃｏ（ＣＨ３ＣＯＯ)２・ｘＨ２Ｏ）、酢酸鉄（III）（Ｆｅ（ＣＨ３ＣＯＯ）３・ｘＨ２Ｏ）、酢酸鉄（II）（Ｆｅ（ＣＨ３ＣＯＯ）２・ｘＨ２Ｏ）；硫酸亜鉛（ＺｎＳＯ４・ｘＨ２Ｏ）、硫酸チタン（Ｔｉ（ＳＯ４）２・ｘＨ２Ｏ）、硫酸ジルコニウム（Ｚｒ（ＳＯ４）２・ｘＨ２Ｏ）、硫酸コバルト（ＣｏＳＯ４・ｘＨ２Ｏ）、硫酸鉄（III）（Ｆｅ２(ＳＯ４）３・ｘＨ２Ｏ）、硫酸鉄（II）（ＦｅＳＯ４・ｘＨ２Ｏ）、硫酸マグネシウム（II）（ＭｇＳＯ４・ｘＨ２Ｏ）；水酸化亜鉛（Ｚｎ（ＯＨ）２・ｘＨ２Ｏ）、水酸化チタン（Ｔｉ（ＯＨ）４・ｘＨ２Ｏ）、水酸化ジルコニウム（Ｚｒ（ＯＨ）４・ｘＨ２Ｏ）、水酸化コバルト（Ｃｏ（ＯＨ）２・ｘＨ２Ｏ）、水酸化鉄（III）（Ｆｅ（ＯＨ）３・ｘＨ２Ｏ）、水酸化
鉄（II）（Ｆｅ（ＯＨ）２・ｘＨ２Ｏ）；臭化亜鉛（ＺｎＢｒ２・ｘＨ２Ｏ）、臭化チタン（ＴｉＢｒ４・ｘＨ２Ｏ）、臭化ジルコニウム（ＺｒＢｒ４・ｘＨ２Ｏ）、臭化コバルト（ＣｏＢｒ２・ｘＨ２Ｏ）、臭化鉄（III）（ＦｅＢｒ３・ｘＨ２Ｏ）、臭化鉄（II）（ＦｅＢｒ２・ｘＨ２Ｏ）；炭酸亜鉛（ＺｎＣＯ３・ｘＨ２Ｏ）、炭酸コバルト（ＣｏＣＯ３・ｘＨ２Ｏ）、炭酸鉄（III）（Ｆｅ２（ＣＯ３）３・ｘＨ２Ｏ）；塩化酸化ジルコニウム（ＺｒＯＣｌ２・ｘＨ２Ｏ）、酢酸モリブデン（II）二量体（（Ｍｏ（ＣＨ３ＣＯＯ）２）２）等が挙げられる。なお、ｘは、０～１２の数である。これらは１種単独で、又は２種以上を混合して用いることができる。
These polyvalent metal ions are supplied in the form of various salts. Specifically, the metal salts include zinc nitrate (Zn(NO 3 ) 2.xH 2 O), titanium nitrate (Ti(NO 3 ) 4.xH 2 O), cobalt nitrate (Co(NO 3 ) 2.xH 2 O), iron(III) nitrate (Fe(NO 3 ) 3 ·xH 2 O), iron(II) nitrate (Fe(NO 3 ) 2 ·xH 2 O), nickel(II) nitrate (Ni(NO 3 ) 2.xH 2 O), copper (II) nitrate ( Cu (NO 3 ) 2.xH 2 O), aluminum (III) nitrate (Al(NO 3 ) 3.xH 2 O), magnesium nitrate (II) (Mg (NO 3 ) 2.xH 2 O); Zinc chloride (ZnCl 2.xH 2 O), titanium chloride (TiCl 4.xH 2 O), zirconium chloride (ZrCl 4.xH 2 O), cobalt chloride (CoCl 2 . xH 2 O), iron (III) chloride (FeCl 3 x H 2 O), iron (II) chloride (FeCl 2 x H 2 O), chromium (III) chloride (CrCl 3 x H 2 O), scandium chloride ( III) ( ScCl3.xH2O ), manganese(II) chloride (MnCl2.xH2O); zinc acetate ( Zn (CH3COO)2.xH2O ) , titanium acetate (Ti( CH3COO )) 4.xH 2 O), zirconium acetate (Zr(CH 3 COO) 4.xH 2 O), cobalt acetate (Co(CH 3 COO) 2.xH 2 O), iron(III) acetate (Fe(CH 3 COO) ) 3.xH 2 O), iron(II) acetate (Fe(CH 3 COO) 2.xH 2 O); zinc sulfate (ZnSO 4.xH 2 O), titanium sulfate (Ti(SO 4 ) 2.xH 2 O), zirconium sulfate (Zr(SO 4 ) 2.xH 2 O), cobalt sulfate (CoSO 4.xH 2 O), iron (III) sulfate (Fe 2 (SO 4 ) 3.xH 2 O), iron sulfate (II) (FeSO 4 x H 2 O), magnesium sulfate (II) (MgSO 4 x H 2 O); zinc hydroxide (Zn(OH) 2 x H 2 O), titanium hydroxide (Ti(OH) 4・xH 2 O), zirconium hydroxide (Zr(OH) 4.xH 2 O), cobalt hydroxide (Co(OH) 2.xH 2 O), iron (III) hydroxide (Fe(OH) 3.xH 2 O), iron(II) hydroxide (Fe(OH) 2.xH 2 O); zinc bromide (ZnBr 2.xH 2 O), titanium bromide (TiBr 4.xH 2 O), zirconium bromide ( ZrBr4.xH2O ), cobalt bromide ( CoBr2.xH2O ), iron ( III ) bromide ( FeBr3.xH2O ), iron ( II) bromide ( FeBr2.xH2O ); Zinc carbonate (ZnCO 3 .xH 2 O), cobalt carbonate (CoCO 3 .xH 2 O), iron (III) carbonate (Fe 2 (CO 3 ) 3 .xH 2 O); zirconium chloride oxide (ZrOCl 2 .xH 2 O), molybdenum (II) acetate dimer ((Mo(CH 3 COO) 2 ) 2 ), and the like. Note that x is a number from 0 to 12. These can be used alone or in combination of two or more.
本発明の金属有機構造体は、式（１）で表わされるカルボン酸イオン以外の有機配位子を補助配位子として含むことができる。金属有機構造体に補助配位子を含有させることで、金属有機構造体に高次構造を導入することができる。そのような補助配位子としては、テレフタル酸、フタル酸、イソフタル酸、５－シアノイソフタル酸、１，３，５－トリメシン酸、１，３，５－トリス（４－カルボキシフェニル）ベンゼン、４，４’－ジカルボキシビフェニル、３，５－ジカルボキシピリジン、２，３－ジカルボキシピラジン、１，３，５－トリス（４－カルボキシフェニル）ベンゼン、１，２，４，５－テトラキス（４－カルボキシフェニル）ベンゼン、９，１０－アントラセンジカルボン酸、２，６－ナフタレンジカルボン酸、［１，１’：４’，１”］ターフェニル－３，３”，５，５”－テトラカルボン酸、ビフェニル－３，３”，５，５”－テトラカルボン酸、３，３’，５，５’－テトラカルボキシジフェニルメタン、１，３，５－トリス（４’－カルボキシ［１，１’－ビフェニル］－４－イル）ベンゼン、１，３，５－トリス（４－カルボキシフェニル）トリアジン、１，２－ビス（４－カルボキシ－３－ニトロフェニル）エテン、１，２－ビス（４－カルボキシ－３－アミノフェニル）エテン、trans,trans－ムコン酸、フマール酸、ベンゾイミダゾール、イミダゾール、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）、ピラジン、４，４’－ジピリジル、１，２－ジ（４－ピリジル）エチレン、１，２－ジ（４－ピリジル）エタン、２，７－ジアザピレン、４，４’－アゾビスピリジン、１，５－ナフチリジン、フェナジン、２ビス（３－（４－ピリジル）－２，４－ペンタンジオナト）銅等が挙げられる。式（１）で表されるカルボン酸イオンと補助配位子を用いる場合の混合モル比は特に制限されない。 The metal-organic structure of the present invention can contain an organic ligand other than the carboxylic acid ion represented by formula (1) as an auxiliary ligand. By including an auxiliary ligand in the metal-organic structure, a higher-order structure can be introduced into the metal-organic structure. Such auxiliary 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-naphthalene dicarboxylic acid, [1,1':4',1'']terphenyl-3,3'',5,5''-tetracarboxylic acid , biphenyl-3,3",5,5"-tetracarboxylic acid, 3,3',5,5'-tetracarboxydiphenylmethane, 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, 1,2-di(4-pyridyl)ethane, 2,7-diazapyrene, 4,4'-azobispyridine, 1,5-naphthyridine, phenazine, 2bis(3- (4-pyridyl)-2,4-pentanedionato) copper, etc. When using the carboxylic acid ion represented by formula (1) and the auxiliary ligand, the mixing molar ratio is not particularly limited.
本発明の金属有機構造体の製造方法として、特に制限されず、溶媒拡散法、溶媒撹拌法、水熱法等の溶液法、反応溶液にマイクロ波を照射して系全体を短時間に均一に加熱するマイクロ波法、反応容器に超音波を照射することにより、反応容器中で圧力の変化が繰り返し起こり、この圧力の変化により、溶媒が気泡を形成し崩壊するキャビテーションと呼ばれる現象がおき、その際に約５０００Ｋ、１００００ｂａｒもの高エネルギー場が局所的に形成される結晶の各生成の反応場となる超音波法、溶媒を用いずに、金属イオン発生源と有機配位子を混合する固相合成法、結晶水程度の水を添加して金属イオン発生源と有機配位子を混合するＬＡＧ（liquid assisted grinding）法等のいずれの方法も用いることができる。 The method for producing the metal-organic structure of the present invention is not particularly limited, and may be a solution method such as a solvent diffusion method, a solvent stirring method, or a hydrothermal method, or by irradiating the reaction solution with microwaves to uniformly produce the entire system in a short time. In the microwave heating method, by irradiating the reaction container with ultrasonic waves, pressure changes occur repeatedly in the reaction container, and this pressure change causes a phenomenon called cavitation, in which the solvent forms bubbles and collapses. Ultrasonic method where a high energy field of about 5000K and 10000 bar is locally formed as a reaction field for each crystal formation, and solid phase which mixes metal ion source and organic ligand without using a solvent. Any method can be used, such as a synthetic method or a LAG (liquid assisted grinding) method in which a metal ion source and an organic ligand are mixed by adding water equivalent to crystallization water.
本発明の金属有機構造体の製造方法としては、例えば、金属イオンの発生源となる金属化合物と溶媒とを含有する第一溶液、式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸と溶媒とを含有する第二溶液、及び、必要に応じて、補助配位子と溶媒とを含有する第三溶液をそれぞれ調製する工程と、第一溶液と、第二溶液及び第三溶液を混合して反応液を調製し、この反応液を加熱することで、金属有機構造体を得る工程と、を備える。第一～第三溶液は別々に調製する必要はなく、例えば、上記金属化合物、式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸、補助配位子となる化合物、溶媒とを１度に混合して１つの溶液を調製してもよい。 The method for producing the metal-organic structure of the present invention includes, for example, a first solution containing a metal compound that is a source of metal ions and a solvent, a carboxylic acid ion represented by formula (1), or a precursor thereof. a step of preparing a second solution containing a certain carboxylic acid and a solvent, and a third solution containing an auxiliary ligand and a solvent as necessary; The method includes a step of preparing a reaction solution by mixing the three solutions, and heating the reaction solution to obtain a metal-organic structure. The first to third solutions do not need to be prepared separately, and include, for example, the above metal compound, the carboxylic acid ion represented by formula (1) or its precursor carboxylic acid, a compound serving as an auxiliary ligand, and a solvent. You may prepare one solution by mixing both at once.
上記金属化合物と式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸との混合モル比は、得られてくる金属有機構造体の細孔サイズ、表面特性に応じて任意に選択することができるが、式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸１モルに対して金属化合物を０．３モル以上用いるのが好ましく、さらに０．５モル以上、さらに１モル以上、さらに１．５モル以上、さらに２モル以上、さらに３モル以上、さらに４モル以上用いるのが好ましい。また、１０モル以下用いるのが好ましい。 The mixing molar ratio of the above metal compound and the carboxylic acid ion represented by formula (1) or its precursor carboxylic acid can be arbitrarily determined depending on the pore size and surface characteristics of the metal-organic structure to be obtained. Although the metal compound can be selected, it is preferable to use 0.3 mol or more of the metal compound per 1 mol of the carboxylic acid ion represented by formula (1) or its precursor, and more preferably 0.5 mol or more. , more preferably 1 mol or more, further 1.5 mol or more, further 2 mol or more, further 3 mol or more, further preferably 4 mol or more. Moreover, it is preferable to use 10 mol or less.
反応液中の上記金属イオンの濃度は、２０～４００ミリモル／Ｌの範囲が好ましい。式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸の反応液中の濃度は、３～２００ミリモル／Ｌの範囲が好ましい。補助配位子の反応液中の濃度は、１０～４００ミリモル／Ｌであるのが好ましい。 The concentration of the metal ions in the reaction solution is preferably in the range of 20 to 400 mmol/L. The concentration of the carboxylic acid ion represented by formula (1) or its precursor carboxylic acid in the reaction solution is preferably in the range of 3 to 200 mmol/L. The concentration of the auxiliary ligand in the reaction solution is preferably 10 to 400 mmol/L.
用いる溶媒としては、特に限定されないが、Ｎ，Ｎ－ジメチルホルムアミド（以下「ＤＭＦ」と記載することがある。）、Ｎ，Ｎ－ジエチルホルムアミド（以下「ＤＥＦ」と記載することがある。）、Ｎ，Ｎ－ジメチルアセトアミド（以下「ＤＭＡ」と記載することがある。）、Ｎ－メチル－２－ピロリドン（以下「ＮＭＰ」と記載することがある。）、ジメチルスルホキシド（以下「ＤＭＳＯ」と記載することがある。）及び水からなる群より選ばれる１種又は２種以上を混合して用いることができる。また、これらの溶媒にメチルアルコール、エチルアルコール等のアルコールを混合して用いてもよい。また、適宜、ギ酸、酢酸、トリフルオロ酢酸、硝酸、テトラフルオロホウ酸、安息香酸等の有機酸又は無機酸、ブチルアミン、トリエチルアミン等の有機アミンなどを適宜添加することができる。 The solvent used is not particularly limited, but 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"), N-methyl-2-pyrrolidone (hereinafter sometimes referred to as "NMP"), dimethyl sulfoxide (hereinafter referred to as "DMSO") ) and water, or a mixture of two or more thereof can be used. Furthermore, alcohols such as methyl alcohol and ethyl alcohol may be mixed with these solvents. Furthermore, organic or inorganic acids such as formic acid, acetic acid, trifluoroacetic acid, nitric acid, tetrafluoroboric acid, and benzoic acid, and organic amines such as butylamine and triethylamine can be added as appropriate.
反応液の加熱温度は、特に制限されないが、例えば、室温～２００℃の範囲、５０～１９０℃の範囲、８０～１６０℃の範囲、９０～１３０℃の範囲等を挙げることができる。また、本発明の金属有機構造体は、上記金属化合物、式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸、必要に応じて補助配位子となる化合物を溶媒中で混合し、これを冷却して－７８℃～室温で静置することにより製造することもできる。各成分の混合方法としては特に制限されず、例えば、金属イオンの発生源となる金属化合物と溶媒とを含有する第一溶液、式（１）で表されるカルボン酸イオン又はその前駆体であるカルボン酸と溶媒とを含有する第二溶液、及び、必要に応じて、補助配位子と溶媒とを含有する第三溶液をそれぞれ調製し、氷冷しながら第一溶液に第二溶液及び必要に応じて第三溶液を添加してもよい。 The heating temperature of the reaction solution is not particularly limited, and examples thereof include a range of room temperature to 200°C, a range of 50 to 190°C, a range of 80 to 160°C, a range of 90 to 130°C. In addition, the metal-organic structure of the present invention can be prepared by combining the metal compound, the carboxylic acid ion represented by formula (1) or its precursor carboxylic acid, and optionally a compound serving as an auxiliary ligand in a solvent. It can also be produced by mixing, cooling and standing at -78°C to room temperature. The method of mixing each component is not particularly limited, and examples thereof include a first solution containing a metal compound that is a source of metal ions and a solvent, a carboxylic acid ion represented by formula (1), or a precursor thereof. A second solution containing a carboxylic acid and a solvent and, if necessary, a third solution containing an auxiliary ligand and a solvent are respectively prepared, and the second solution and the necessary solution are added to the first solution while cooling on ice. A third solution may be added depending on the conditions.
本発明のガス貯蔵剤は、本発明の金属有機構造体を含む。本発明のガス貯蔵剤は、本発明の金属有機構造体のみからなっていてもよく、ガス貯蔵剤としての使用に支障をきたさない範囲で他の成分を含んでもよい。本発明のガス貯蔵剤の形状は特に制限されず、例えば、粉状、顆粒状、ペレット状等を挙げることができる。本発明の金属有機構造体は、水素、メタン、アセチレン、二酸化炭素、窒素等のガスを吸着または吸蔵することで、前記ガスを貯蔵することができる。本発明の金属有機構造体を用いたガスの貯蔵方法は、特に制限されないが、本発明の金属有機構造体とガスを接触させる方法が好ましく、接触させる方法は、特に制限されない。例えば、タンク中に、本発明の金属有機構造体を充填してガス貯蔵タンクとし、該タンク内にガスを流入する方法、タンクの内壁を構成する表面に本発明の金属有機構造体を担持させてガス貯蔵タンクとし、該タンク内にガスを流入する方法、タンクを本発明の金属有機構造体を含む材料で成形してガス貯蔵タンクとし、該タンク内にガスを流入する方法等を挙げることができる。 The gas storage agent of the present invention comprises the metal-organic framework of the present invention. The gas storage agent of the present invention may consist only of the metal-organic structure of the present invention, or may contain other components as long as they do not interfere with use as a gas storage agent. The shape of the gas storage agent of the present invention is not particularly limited, and examples thereof include powder, granule, and pellet shape. The metal-organic structure 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 structure of the present invention is not particularly limited, but a method of contacting the gas with the metal-organic structure of the present invention is preferable, and the method of contacting the gas is not particularly limited. For example, a method of filling a tank with the metal-organic structure of the present invention to form a gas storage tank and flowing gas into the tank, and a method of supporting the metal-organic structure of the present invention on the surface constituting the inner wall of the tank. Examples include a method of forming a gas storage tank by forming a gas storage tank and flowing gas into the tank, and a method of molding a tank with a material containing the metal-organic structure of the present invention to form a gas storage tank and flowing gas into the tank. Can be done.
以下、本発明の実施例を挙げて、本発明を具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。本発明の金属有機構造体を構成する式（１）で表されるカルボン酸イオンの前駆体となるカルボン酸として、以下の表１に示す有機配位子１～３３を用いた。 Hereinafter, the present invention will be specifically explained with reference to Examples, but the technical scope of the present invention is not limited to these examples. Organic ligands 1 to 33 shown in Table 1 below were used as carboxylic acids serving as precursors of carboxylic acid ions represented by formula (1) constituting the metal-organic structure of the present invention.
［製造例１］有機配位子１の合成
国際公開ＷＯ００／２０３７２の実施例１記載の方法と同様の方法で、有機配位子１を得た。
[Production Example 1] Synthesis of Organic Ligand 1 Organic Ligand 1 was obtained in the same manner as described in Example 1 of International Publication WO 00/20372.
［製造例２］有機配位子２の合成
２－（４－Ｂｒｏｍｏｐｈｅｎｙｌ）－１，３－ｄｉｏｘｏｌａｎｅ（４．０ｇ，１７．５ｍｍｏｌ）のテトラヒドロフラン（ＴＨＦ）（５０ｍＬ）溶液に窒素雰囲気で－７８°Ｃで２．７６Ｍのｎ－ＢｕＬｉヘキサン溶液６．７ｍＬ（１８．４ｍｍｏｌ）をゆっくりと加え、同温度で1時間撹拌した。ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅ０．
８５ｇ（４．３８ｍｍｏｌ）のＴＨＦ（５０ｍＬ）溶液を同温度で加え、ゆっくりと室温まで昇温しながら１０時間撹拌した。溶液を水にあけ、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄後、硫酸マグネシウムで乾燥した。ろ過後、溶媒を減圧留去した。得られた残渣をアセトン５０ｍＬに溶解し、１Ｎ塩酸１０ｍＬを加え、２時間加熱還流下に撹拌した。溶媒を減圧留去し、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。ろ過後、有機溶媒を減圧留去した。得られた残渣を、ジオキサン１００ｍＬ、水２５ｍＬに溶解し、ＫＭｎＯ４４．２ｇ（２６．６ｍｍｏｌ）を加え、室温で２４時間撹拌した。溶液をセライトろ過後、溶媒を減圧留去し、残渣に濃塩酸を加え、溶液をｐＨ３以下とした。析出した固体をろ過後、水で洗浄し、減圧下加熱乾燥し、有機配位子２を得た。
[Production Example 2] Synthesis of Organic Ligand 2 A solution of 2-(4-Bromophenyl)-1,3-dioxolane (4.0 g, 17.5 mmol) in tetrahydrofuran (THF) (50 mL) was heated at -78° in a nitrogen atmosphere. 6.7 mL (18.4 mmol) of a 2.76 M n-BuLi hexane solution was slowly added at C and stirred at the same temperature for 1 hour. dimethyl terephthalate0.
A solution of 85 g (4.38 mmol) in THF (50 mL) was added at the same temperature, and the mixture was stirred for 10 hours while slowly raising the temperature to room temperature. The solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 50 mL of acetone, 10 mL of 1N hydrochloric acid was added, and the mixture was stirred under heating under reflux for 2 hours. The solvent was distilled off under reduced pressure, extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over magnesium sulfate. After filtration, the organic solvent was distilled off under reduced pressure. The obtained residue was dissolved in 100 mL of dioxane and 25 mL of water, 4.2 g (26.6 mmol) of KMnO 4 was added, and the mixture was stirred at room temperature for 24 hours. After filtering the solution through Celite, the solvent was distilled off under reduced pressure, and concentrated hydrochloric acid was added to the residue to adjust the pH of the solution to 3 or less. The precipitated solid was filtered, washed with water, and dried under reduced pressure to obtain organic ligand 2.
［製造例３］有機配位子３の合成
得られた有機配位子２（１．０ｇ、１．６２ｍｍｏｌ）のトリフルオロ酢酸溶液に、トリエチルシラン４０ｍｇ（３．４０ｍｍｏｌ）を室温で加え、室温で１０時間撹拌した。溶液を水にあけ、得られた固体をろ過後、水で洗浄した。得られた固体を１０Ｎ水酸化ナトリウム水溶液に溶解後、溶液をジエチルエーテルで洗浄し、さらに濃塩酸を加え、溶液のｐＨを３以下とした。析出した固体をろ過後、水で洗浄し、減圧下に加熱乾燥し、有機配位子３を得た。
[Production Example 3] Synthesis of Organic Ligand 3 40 mg (3.40 mmol) of triethylsilane was added to a trifluoroacetic acid solution of the obtained organic ligand 2 (1.0 g, 1.62 mmol) at room temperature. The mixture was stirred for 10 hours. The solution was poured into water, and the resulting solid was filtered and washed with water. After dissolving the obtained solid in a 10N aqueous sodium hydroxide solution, the solution was washed with diethyl ether, and concentrated hydrochloric acid was added to adjust the pH of the solution to 3 or less. The precipitated solid was filtered, washed with water, and dried under reduced pressure to obtain organic ligand 3.
［製造例４］有機配位子４の合成
得られた有機配位子２のメタノール溶液に触媒量の濃硫酸を加え、還流下、１０時間加熱撹拌した。溶媒を減圧留去し、酢酸エチルで抽出、有機層を飽和食塩水で洗浄後、硫酸マグネシウムで乾燥した。ろ過後、溶媒を減圧留去した。得られた残渣をメタノールに溶解し、５Ｎ水酸化ナトリウム溶液（用いた有機配位子２に対して、２０モル当量）を加え、室温で１０１０時間撹拌した。溶媒を減圧留去し、濃塩酸を加えて溶液のｐＨを３以下にした。析出した固体をろ過後、水で洗浄し、減圧下に加熱乾燥し、有機配位子４を得た。
[Production Example 4] Synthesis of Organic Ligand 4 A catalytic amount of concentrated sulfuric acid was added to a methanol solution of the obtained organic ligand 2, and the mixture was heated and stirred under reflux for 10 hours. The solvent was distilled off under reduced pressure, extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The obtained residue was dissolved in methanol, 5N sodium hydroxide solution (20 molar equivalents relative to the organic ligand 2 used) was added, and the mixture was stirred at room temperature for 1010 hours. The solvent was distilled off under reduced pressure, and concentrated hydrochloric acid was added to adjust the pH of the solution to 3 or less. The precipitated solid was filtered, washed with water, and dried under reduced pressure to obtain organic ligand 4.
［製造例５］有機配位子５の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ｉｓｏｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子５を得た。
[Production Example 5] Synthesis of Organic Ligand 5 Organic ligand 5 was obtained in the same manner as Production Example 2 except that dimethyl isophthalate was used instead of dimethyl terephthalate.
［製造例６］有機配位子６の合成
有機配位子２の代わりに有機配位子５を用いる以外は製造例３と同様に行い、有機配位子６を得た。
[Production Example 6] Synthesis of Organic Ligand 6 Organic Ligand 6 was obtained in the same manner as Production Example 3 except that Organic Ligand 5 was used instead of Organic Ligand 2.
［製造例７］有機配位子７の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ５－ｍｅｔｈｙｌｉｓｏｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子７を得た。
[Production Example 7] Synthesis of Organic Ligand 7 Organic ligand 7 was obtained in the same manner as Production Example 2 except that dimethyl 5-methylisophthalate was used instead of dimethyl terephthalate.
［製造例８］有機配位子８の合成
有機配位子２の代わりに有機配位子７を用いる以外は製造例３と同様に行い、有機配位子８を得た。
[Production Example 8] Synthesis of Organic Ligand 8 Organic Ligand 8 was obtained in the same manner as Production Example 3 except that Organic Ligand 7 was used instead of Organic Ligand 2.
［製造例９］有機配位子９の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ５－ｍｅｔｈｏｘｙｌｉｓｏｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子９を得た。
[Production Example 9] Synthesis of Organic Ligand 9 Organic ligand 9 was obtained in the same manner as Production Example 2 except that dimethyl 5-methoxylisophthalate was used instead of dimethyl terephthalate.
［製造例１０］有機配位子１０の合成
有機配位子２の代わりに有機配位子１３を用いる以外は製造例３と同様に行い、有機配位子１０を得た。有機配位子１３の合成方法は後述する。
[Production Example 10] Synthesis of Organic Ligand 10 Organic ligand 10 was obtained in the same manner as Production Example 3 except that organic ligand 13 was used instead of organic ligand 2. The method for synthesizing organic ligand 13 will be described later.
［製造例１１］有機配位子１１の合成
有機配位子２の代わりに有機配位子１４を用いる以外は製造例３と同様に行い、有機配位子１１を得た。有機配位子１４の合成方法は後述する。
[Production Example 11] Synthesis of Organic Ligand 11 Organic ligand 11 was obtained in the same manner as Production Example 3 except that organic ligand 14 was used instead of organic ligand 2. The method for synthesizing organic ligand 14 will be described later.
［製造例１２］有機配位子１２の合成
有機配位子２の代わりに有機配位子１５を用いる以外は製造例３と同様に行い、有機配位子１２を得た。有機配位子１５の合成方法は後述する。
[Production Example 12] Synthesis of Organic Ligand 12 Organic Ligand 12 was obtained in the same manner as Production Example 3 except that Organic Ligand 15 was used instead of Organic Ligand 2. The method for synthesizing organic ligand 15 will be described later.
［製造例１３］有機配位子１３の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉｍｅｔｈｙｌｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子１３を得た。
[Production Example 13] Synthesis of Organic Ligand 13 Organic ligand 13 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-dimethylterephthalate was used instead of dimethyl terephthalate.
［製造例１４］有機配位子１４の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉｅｔｈｙｌｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子１４を得た。
[Production Example 14] Synthesis of Organic Ligand 14 Organic ligand 14 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-diethylterephthalate was used instead of dimethyl terephthalate.
［製造例１５］有機配位子１５の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉ（１－ｐｒｏｐｙｌ）ｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子１５を得た。
[Production Example 15] Synthesis of Organic Ligand 15 Organic ligand 15 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-di(1-propyl) terephthalate was used instead of dimethyl terephthalate. .
［製造例１６］有機配位子１６の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉ（２－ｐｒｏｐｙｌ）ｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子１６を得た。
[Production Example 16] Synthesis of Organic Ligand 16 Organic ligand 16 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-di(2-propyl) terephthalate was used instead of dimethyl terephthalate. .
［製造例１７］有機配位子１７の合成
有機配位子２の代わりに有機配位子１６を用いる以外は製造例３と同様に行い、有機配位子１７を得た。
[Production Example 17] Synthesis of Organic Ligand 17 Organic Ligand 17 was obtained in the same manner as Production Example 3 except that Organic Ligand 16 was used instead of Organic Ligand 2.
［製造例１８］有機配位子１８の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｔｒｉｍｅｔｈｙｌ １，３，５－ｂｅｎｚｅｎｅｔｒｉｃａｒｂｏｘｙｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子１８を得た。
[Production Example 18] Synthesis of Organic Ligand 18 Organic ligand 18 was obtained in the same manner as Production Example 2 except that trimethyl 1,3,5-benzenetricarboxylate was used instead of dimethyl terephthalate.
［製造例１９］有機配位子１９の合成
有機配位子２の代わりに有機配位子１８を用いる以外は製造例３と同様に行い、有機配位子１９を得た。
[Production Example 19] Synthesis of Organic Ligand 19 Organic ligand 19 was obtained in the same manner as Production Example 3 except that Organic Ligand 18 was used instead of Organic Ligand 2.
［製造例２０］有機配位子２０の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉｅｔｈｏｘｙｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２０を得た。
[Production Example 20] Synthesis of Organic Ligand 20 Organic ligand 20 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-diethoxyterephthalate was used instead of dimethyl terephthalate.
［製造例２１］有機配位子２１の合成
有機配位子２の代わりに有機配位子２０を用いる以外は製造例３と同様に行い、有機配位子２１を得た。
[Production Example 21] Synthesis of Organic Ligand 21 Organic Ligand 21 was obtained in the same manner as Production Example 3 except that Organic Ligand 20 was used instead of Organic Ligand 2.
［製造例２２］有機配位子２３の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉ（ｎ－ｐｒｏｐｏｘｙ）ｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２３を得た。
[Production Example 22] Synthesis of Organic Ligand 23 Organic ligand 23 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-di(n-propoxy) terephthalate was used instead of dimethyl terephthalate. .
［製造例２３］有機配位子２２の合成
有機配位子２の代わりに有機配位子２３を用いる以外は製造例３と同様に行い、有機配位子２２を得た。
[Production Example 23] Synthesis of Organic Ligand 22 Organic Ligand 22 was obtained in the same manner as Production Example 3 except that Organic Ligand 23 was used instead of Organic Ligand 2.
［製造例２４］有機配位子２４の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉｍｅｔｈｏｘｙｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２４を得た。
[Production Example 24] Synthesis of Organic Ligand 24 Organic ligand 24 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-dimethoxyterephthalate was used instead of dimethyl terephthalate.
［製造例２５］有機配位子２５の合成
有機配位子２の代わりに有機配位子２４を用いる以外は製造例３と同様に行い、有機配位子２５を得た。
[Production Example 25] Synthesis of Organic Ligand 25 Organic Ligand 25 was obtained in the same manner as Production Example 3 except that Organic Ligand 24 was used instead of Organic Ligand 2.
［製造例２６］有機配位子２６合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉｐｈｅｎｙｌｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２６を得た。
[Production Example 26] Synthesis of Organic Ligand 26 Organic ligand 26 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-diphenylterephthalate was used instead of dimethyl terephthalate.
［製造例２７］有機配位子２７合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，５－ｄｉ（ｉｓｏｐｒｏｐｏｘｙ）ｔｅｒｅｐｈｔｈａｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２７を得た。
[Production Example 27] Synthesis of Organic Ligand 27 Organic ligand 27 was obtained in the same manner as Production Example 2 except that dimethyl 2,5-di(isopropoxy) terephthalate was used instead of dimethyl terephthalate.
［製造例２８］有機配位子２８の合成
有機配位子２の代わりに有機配位子２７を用いる以外は製造例３と同様に行い、有機配位子２８を得た。
[Production Example 28] Synthesis of Organic Ligand 28 Organic Ligand 28 was obtained in the same manner as Production Example 3 except that Organic Ligand 27 was used instead of Organic Ligand 2.
［製造例２９］有機配位子２９の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｂｕｔｙｌ ４，４’－ｂｉｐｈｅｎｙｌｄｉｃａｒｂｏｘｙｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子２９を得た。
[Production Example 29] Synthesis of Organic Ligand 29 Organic ligand 29 was obtained in the same manner as Production Example 2 except that dibutyl 4,4'-biphenyl dicarboxylate was used instead of dimethyl terephthalate.
［製造例３０］有機配位子３０の合成
有機配位子２の代わりに有機配位子２９を用いる以外は製造例３と同様に行い、有機配位子３０を得た。
[Production Example 30] Synthesis of Organic Ligand 30 Organic ligand 30 was obtained in the same manner as Production Example 3 except that Organic Ligand 29 was used instead of Organic Ligand 2.
［製造例３１］有機配位子３１の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、４，４’－ｂｉｓ（ｍｅｔｈｏｘｙｃａｒｂｏｎｙｌ）ｄｉｐｈｅｎｙｌｅｔｈｅｒを用いる以外は製造例２と同様に行い、下記中間体Ａを得た。
[Production Example 31] Synthesis of Organic Ligand 31 The following Intermediate A was obtained in the same manner as Production Example 2, except that 4,4'-bis (methoxycarbonyl) diphenylether was used instead of dimethyl terephthalate.
有機配位子２の代わりに中間体Ａを用いる以外は製造例３と同様に行い、有機配位子３１を得た。 Organic ligand 31 was obtained in the same manner as in Production Example 3 except that Intermediate A was used instead of organic ligand 2.
［製造例３２］有機配位子３２の合成
ｄｉｍｅｔｈｙｌ ｔｅｒｅｐｈｔｈａｌａｔｅの代わりに、ｄｉｍｅｔｈｙｌ ２，６－ｎａｐｈｔｈａｌｅｎｅｄｉｃａｒｂｏｘｙｌａｔｅを用いる以外は製造例２と同様に行い、有機配位子３２を得た。
[Production Example 32] Synthesis of Organic Ligand 32 Organic ligand 32 was obtained in the same manner as Production Example 2 except that dimethyl 2,6-naphthalene dicarboxylate was used instead of dimethyl terephthalate.
［製造例３３］有機配位子３３の合成
有機配位子２の代わりに有機配位子３２を用いる以外は製造例３と同様に行い、有機配位子３３を得た。
[Production Example 33] Synthesis of Organic Ligand 33 Organic ligand 33 was obtained in the same manner as Production Example 3 except that organic ligand 32 was used instead of organic ligand 2.
得られた有機配位子の１Ｈ－ＮＭＲデータを以下に示す。
有機配位子２
1HNMR(DMSO-d6) δ 12.94(brs, 4H), 7.88(d, 8H), 7.33(d, 8H), 7.16(s, 4H), 6.76(s,2H)
有機配位子３
1HNMR(DMSO-d6) δ 12.8(brs, 4H), 7.89(d, 8H), 7.24(d, 8H), 7.09(s, 4H), 5.79(s, 2H)
有機配位子４
1HNMR(DMSO-d6) δ 1.95(brs, 4H), 7.91(d, 8H). 7.50(d, 8H), 7.35(s, 4H), 2.94(s, 6H), 7.082(d, 4H), 6.715(brs, 2H)
有機配位子５
1HNMR(DMSO-d6) δ 12.885(brs, 4H), 7.831(d, 8H), 7.247(d, 9H), 7,203(s, 1H)
有機配位子６
1HNMR(DMSO-d6) δ 7.853(d, 8H), 7,290(m, 1H), 7.175(d, 8H), 6.984-6.960(m, 3H), 5.778(s, 2H)
有機配位子７
1HNMR(DMSO-d6) δ 7.822(d, 8H), 7.254(d, 8H), 6.943(s, 2H), 6.912(s, 1H), 6.664(s, 2H), 2.181(s, 3H)
有機配位子８
1HNMR(DMSO-d6) δ 12.863(brs, 4H), 7.860(d, 8H), 7.169(d, 8H), 6.796(s, 2H), 6.763(s, 1H), 6,723(s, 2H), 2.177(s, 3H)
有機配位子９
1HNMR(DMSO-d6) δ 7.821(d, 8H), 7.244(d, 8H),6.715(s, 3H), 6.614(s, 2H),3.587(s, 3H)
有機配位子１０
1HNMR(DMSO-d6) δ 12.855(brs, 4H), 7.871(d, 8H), 7.177(d, 8H), 6.545(s, 2H), 5.840(s, 2H), 1.992(s, 6H)
有機配位子１１
1HNMR(DMSO-d6) δ 12.886(brs, 4H), 7.886(d, 8H), 7.185(d, 8H), 6.618(s, 2H), 5.910(s, 2H), 2.408(q, 4H). 0.817(t, 6H)
有機配位子１２
1HNMR(DMSO-d6) δ 12.869(brs, 4H), 7.879(d, 8H), 7.175(d, 8H), 6.609(s, 2H), 5.893(s, 2H), 2.375(t, 4H). 1.212(m, 4H), 0.671(t, 6H)
有機配位子１３
1HNMR(DMSO-d6) δ 12.899(brs, 4H), 7.891(d, 8H), 7.341(d, 8H), 6.723(s, 2H), 6.404(s, 2H), 1.777(s, 6H)
有機配位子１４
1HNMR(DMSO-d6) δ 12.908(brs, 4H), 7.889(d, 8H), 7.331(d, 8H), 6.769(s, 2H), 6.470(s, 2H), 2.223(q, 4H). 0.575(t, 6H)
有機配位子１５
1HNMR(DMSO-d6) δ 12.913(brs, 4H), 7.894(d, 8H), 7.334(d, 8H), 6.77(s, 2H), 6.492(s, 2H), 2.207(t, 4H). 0.966(m, 4H), 0.448(t, 6H)
有機配位子１６
1HNMR(DMSO-d6) δ 12.893(brs, 4H), 7.903(d, 8H), 7.325(d, 8H), 6.818(s, 2H), 6.463(s, 2H), 3.090(m, 2H), 0.540(t, 12H)
有機配位子１７
1HNMR(DMSO-d6) δ 12.892(brs, 4H), 7.893(d, 8H), 7.175(d, 8H), 6.659(s, 2H), 6.004(s, 2H), 3.040(m, 2H), 0.766(t, 12H)
有機配位子１８
1HNMR(DMSO-d6) δ 7.776(d, 12H), 7.187(d, 12H), 7.070(s, 1H), 6.652(s, 1H)
有機配位子１９
1HNMR(DMSO-d6) δ 7.802(d, 12H), 7.085(d, 12H), 6.786(s, 3H), 5,717(s, 3H)
有機配位子２０
1HNMR(DMSO-d6) δ 12.894(brs, 4H), 7.857(d, 8H), 7.379(d, 8H), 6.974(s, 2H), 6.233(s, 2H), 3.522(q, 4H), 0.661(t, 6H)
有機配位子２１
1HNMR(DMSO-d6) δ 12.920(brs, 4H), 7.869(d, 8H), 7.217(d, 8H), 6.450(s, 2H), 5.877(s, 2H), 3.564(q, 4H), 0.948(t, 6H)
有機配位子２２
1HNMR(DMSO-d6) δ 12.876(brs, 4H), 7.872(d, 8H), 7.211(d, 8H), 6.421(s, 2H), 5.882(s, 2H), 3.449(t, 6H), 1.372(m, 4H), 0.638(t, 6H)
有機配位子２３
1HNMR(DMSO-d6) δ 12.857(brs, 4H), 7.876(d, 8H), 7.397(d, 8H), 7.003(s, 2H), 6.234(s, 2H), 4.112(t, 6H), 1.137(m, 4H), 0.477(t, 6H)
有機配位子２４
1HNMR(DMSO-d6) δ 12.899brs, 4H), 7.861(d, 8H), 7.347(d, 8H), 6.976(s, 2H), 6.300(s, 2H), 3.203(s, 6H)
有機配位子２５
1HNMR(DMSO-d6) δ 12.885(brs, 4H), 7.876(d, 8H), 7.212(d, 8H), 6.492(s, 2H), 5.911(s, 2H), 3.396(s, 6H)
有機配位子２６
1HNMR(DMSO-d6) δ 12.649(brs, 4H), 7.702(d, 8H), 7.310(d, 8H), 6.90-6.80(m, 10H) 6.809(s, 2H), 6.693(s, 2H)
有機配位子２７
1HNMR(DMSO-d6) δ 12.887(brs, 4H), 7.865(d, 8H), 7.375(d, 8H), 6.815(s, 2H), 6.130(s, 2H), 4.064(m, 2H), 0.708(d, 12H)
有機配位子２８
1HNMR(DMSO-d6) δ 12.898(brs, 4H), 7.870(d, 8H), 7.202(d, 8H), 6.659(s, 2H), 6.004(s, 2H), 4.058(m, 2H), 0.853(d, 12H)
有機配位子２９
1HNMR(DMSO-d6) δ 12.905(brs, 4H), 7.984(d, 8H), 7.620(d, 4H). 7.377(d, 8H), 7.267(d, 4H), 6.827(s, 2H)
有機配位子３０
1HNMR(DMSO-d6) δ 12.873(brs, 4H), 7.898(d, 8H), 7.609(d, 4H). 7.269(d, 8H), 7.194(d, 4H), 5.854(s, 2H)
有機配位子３１
1HNMR(DMSO-d6) δ 12.860(brs, 4H), 7.884(d, 8H), 7.235(d, 8H), 7.106(d, 4H), 6.971(d, 4H) 5.798(s, 2H)
有機配位子３２
1HNMR(DMSO-d6) δ 12.906(brs, 4H), 7.891(d, 8H), 7.776(d, 2H), 7.611(s, 2H), 7.390-7.370(m. 10H) 6.914(s, 2H)
有機配位子３３
1HNMR(DMSO-d6) δ 12.994(brs, 4H), 7.905(d, 8H), 7.7780(d, 2H), 7,542(s, 2H), 7,272(d, 10H), 5.973(s, 2H)
1H-NMR data of the obtained organic ligand is shown below.
organic ligand 2
1HNMR(DMSO-d6) δ 12.94(brs, 4H), 7.88(d, 8H), 7.33(d, 8H), 7.16(s, 4H), 6.76(s,2H)
organic ligand 3
1HNMR(DMSO-d6) δ 12.8(brs, 4H), 7.89(d, 8H), 7.24(d, 8H), 7.09(s, 4H), 5.79(s, 2H)
organic ligand 4
1HNMR(DMSO-d6) δ 1.95(brs, 4H), 7.91(d, 8H). 7.50(d, 8H), 7.35(s, 4H), 2.94(s, 6H), 7.082(d, 4H), 6.715 (brs, 2H)
organic ligand 5
1HNMR(DMSO-d6) δ 12.885(brs, 4H), 7.831(d, 8H), 7.247(d, 9H), 7,203(s, 1H)
organic ligand 6
1HNMR(DMSO-d6) δ 7.853(d, 8H), 7,290(m, 1H), 7.175(d, 8H), 6.984-6.960(m, 3H), 5.778(s, 2H)
organic ligand 7
1HNMR(DMSO-d6) δ 7.822(d, 8H), 7.254(d, 8H), 6.943(s, 2H), 6.912(s, 1H), 6.664(s, 2H), 2.181(s, 3H)
organic ligand 8
1HNMR(DMSO-d6) δ 12.863(brs, 4H), 7.860(d, 8H), 7.169(d, 8H), 6.796(s, 2H), 6.763(s, 1H), 6,723(s, 2H), 2.177 (s, 3H)
organic ligand 9
1HNMR(DMSO-d6) δ 7.821(d, 8H), 7.244(d, 8H),6.715(s, 3H), 6.614(s, 2H),3.587(s, 3H)
organic ligand 10
1HNMR(DMSO-d6) δ 12.855(brs, 4H), 7.871(d, 8H), 7.177(d, 8H), 6.545(s, 2H), 5.840(s, 2H), 1.992(s, 6H)
organic ligand 11
1HNMR(DMSO-d6) δ 12.886(brs, 4H), 7.886(d, 8H), 7.185(d, 8H), 6.618(s, 2H), 5.910(s, 2H), 2.408(q, 4H). 0.817 (t, 6H)
organic ligand 12
1HNMR(DMSO-d6) δ 12.869(brs, 4H), 7.879(d, 8H), 7.175(d, 8H), 6.609(s, 2H), 5.893(s, 2H), 2.375(t, 4H). 1.212 (m, 4H), 0.671(t, 6H)
organic ligand 13
1HNMR(DMSO-d6) δ 12.899(brs, 4H), 7.891(d, 8H), 7.341(d, 8H), 6.723(s, 2H), 6.404(s, 2H), 1.777(s, 6H)
organic ligand 14
1HNMR(DMSO-d6) δ 12.908(brs, 4H), 7.889(d, 8H), 7.331(d, 8H), 6.769(s, 2H), 6.470(s, 2H), 2.223(q, 4H). 0.575 (t, 6H)
organic ligand 15
1HNMR(DMSO-d6) δ 12.913(brs, 4H), 7.894(d, 8H), 7.334(d, 8H), 6.77(s, 2H), 6.492(s, 2H), 2.207(t, 4H). 0.966 (m, 4H), 0.448(t, 6H)
organic ligand 16
1HNMR(DMSO-d6) δ 12.893(brs, 4H), 7.903(d, 8H), 7.325(d, 8H), 6.818(s, 2H), 6.463(s, 2H), 3.090(m, 2H), 0.540 (t, 12H)
organic ligand 17
1HNMR(DMSO-d6) δ 12.892(brs, 4H), 7.893(d, 8H), 7.175(d, 8H), 6.659(s, 2H), 6.004(s, 2H), 3.040(m, 2H), 0.766 (t, 12H)
organic ligand 18
1HNMR(DMSO-d6) δ 7.776(d, 12H), 7.187(d, 12H), 7.070(s, 1H), 6.652(s, 1H)
organic ligand 19
1HNMR(DMSO-d6) δ 7.802(d, 12H), 7.085(d, 12H), 6.786(s, 3H), 5,717(s, 3H)
organic ligand 20
1HNMR(DMSO-d6) δ 12.894(brs, 4H), 7.857(d, 8H), 7.379(d, 8H), 6.974(s, 2H), 6.233(s, 2H), 3.522(q, 4H), 0.661 (t, 6H)
organic ligand 21
1HNMR(DMSO-d6) δ 12.920(brs, 4H), 7.869(d, 8H), 7.217(d, 8H), 6.450(s, 2H), 5.877(s, 2H), 3.564(q, 4H), 0.948 (t, 6H)
organic ligand 22
1HNMR(DMSO-d6) δ 12.876(brs, 4H), 7.872(d, 8H), 7.211(d, 8H), 6.421(s, 2H), 5.882(s, 2H), 3.449(t, 6H), 1.372 (m, 4H), 0.638(t, 6H)
organic ligand 23
1HNMR(DMSO-d6) δ 12.857(brs, 4H), 7.876(d, 8H), 7.397(d, 8H), 7.003(s, 2H), 6.234(s, 2H), 4.112(t, 6H), 1.137 (m, 4H), 0.477(t, 6H)
organic ligand 24
1HNMR(DMSO-d6) δ 12.899brs, 4H), 7.861(d, 8H), 7.347(d, 8H), 6.976(s, 2H), 6.300(s, 2H), 3.203(s, 6H)
organic ligand 25
1HNMR(DMSO-d6) δ 12.885(brs, 4H), 7.876(d, 8H), 7.212(d, 8H), 6.492(s, 2H), 5.911(s, 2H), 3.396(s, 6H)
organic ligand 26
1HNMR(DMSO-d6) δ 12.649(brs, 4H), 7.702(d, 8H), 7.310(d, 8H), 6.90-6.80(m, 10H) 6.809(s, 2H), 6.693(s, 2H)
organic ligand 27
1HNMR(DMSO-d6) δ 12.887(brs, 4H), 7.865(d, 8H), 7.375(d, 8H), 6.815(s, 2H), 6.130(s, 2H), 4.064(m, 2H), 0.708 (d, 12H)
organic ligand 28
1HNMR(DMSO-d6) δ 12.898(brs, 4H), 7.870(d, 8H), 7.202(d, 8H), 6.659(s, 2H), 6.004(s, 2H), 4.058(m, 2H), 0.853 (d, 12H)
organic ligand 29
1HNMR(DMSO-d6) δ 12.905(brs, 4H), 7.984(d, 8H), 7.620(d, 4H). 7.377(d, 8H), 7.267(d, 4H), 6.827(s, 2H)
organic ligand 30
1HNMR(DMSO-d6) δ 12.873(brs, 4H), 7.898(d, 8H), 7.609(d, 4H). 7.269(d, 8H), 7.194(d, 4H), 5.854(s, 2H)
organic ligand 31
1HNMR(DMSO-d6) δ 12.860(brs, 4H), 7.884(d, 8H), 7.235(d, 8H), 7.106(d, 4H), 6.971(d, 4H) 5.798(s, 2H)
organic ligand 32
1HNMR(DMSO-d6) δ 12.906(brs, 4H), 7.891(d, 8H), 7.776(d, 2H), 7.611(s, 2H), 7.390-7.370(m. 10H) 6.914(s, 2H)
organic ligand 33
1HNMR(DMSO-d6) δ 12.994(brs, 4H), 7.905(d, 8H), 7.7780(d, 2H), 7,542(s, 2H), 7,272(d, 10H), 5.973(s, 2H)
［実施例１］
有機配位子１（６０ｍｍｇ、０．１１８ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１７７ｍｇ、０．４７２ｍｍｏｌ）をＤＭＦ９．４ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１４４時間加熱した。得られた溶液を遠心分離し、上澄みの溶媒をデカントし、固体を分離した。得られた固体にＤＭＦを添加し、遠心分離で溶媒を分離する操作を３回繰り返して、固体を洗浄し、さらにＤＭＦ中に１晩浸漬した。さらに遠心分離して、溶媒を分離し、溶媒をクロロホルムに代えて、同様の洗浄作業を３回行い、クロロホルム中に１晩浸漬した。さらに遠心分離して、溶媒から固体を分離し、減圧下１５０℃で６時間加熱乾燥して目的とする金属有機構造体ＭＯＦ１をオフホワイトの固体（４８ｍｇ）として得た。
[Example 1]
Organic ligand 1 (60 mmg, 0.118 mmol) and metal salt Al(NO 3 ) 3.9H 2 O (177 mg, 0.472 mmol) were dissolved in 9.4 mL of DMF, filtered through a membrane filter, and placed in a sealed vial. The mixture was heated at 120° C. for 144 hours. The resulting solution was centrifuged, the supernatant solvent was decanted, and the solids were separated. The operation of adding DMF to the obtained solid and separating the solvent by centrifugation was repeated three times to wash the solid, and then immersed in DMF overnight. Further centrifugation was performed to separate the solvent, the same washing operation was performed three times by replacing the solvent with chloroform, and the sample was immersed in chloroform overnight. Further centrifugation was performed to separate the solid from the solvent, followed by heating and drying at 150° C. for 6 hours under reduced pressure to obtain the desired metal-organic framework MOF1 as an off-white solid (48 mg).
［実施例２］
溶媒としてＤＭＦ９．４ｍＬにトリフルオロ酢酸０．５ｍＬを添加した以外は、実施例１と同様に行いＭＯＦ２を白色の固体（４２ｍｇ）として得た。
[Example 2]
The same procedure as in Example 1 was performed except that 0.5 mL of trifluoroacetic acid was added to 9.4 mL of DMF as a solvent to obtain MOF2 as a white solid (42 mg).
［実施例３］
有機配位子１（６４．８ｍｍｇ、０．１２７ｍｍｏｌ）と金属塩としてＡｌＣｌ３・６Ｈ２Ｏ（１６０ｍｇ、０．６６２ｍｍｏｌ）をＤＭＦ２８ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で２４時間加熱する以外は実施例１と同様に行いＭＯＦ３を白色の固体（７７ｍｇ）として得た。
[Example 3]
Organic ligand 1 (64.8 mmg, 0.127 mmol) and AlCl 3.6H 2 O (160 mg, 0.662 mmol) as a metal salt were dissolved in 28 mL of DMF, filtered through a membrane filter, and then heated at 120°C in a sealed vial. The same procedure as in Example 1 was carried out except that the mixture was heated for 24 hours to obtain MOF3 as a white solid (77 mg).
［実施例４］
金属塩としてＣｒ（ＮＯ３）３・９Ｈ２Ｏ（１８８ｍｇ、０．４７２ｍｍｏｌ）を用い、溶媒としてＤＭＦ２４ｍＬ及びトリフルオロ酢酸１ｍＬを用い、９０℃で７２時間、１２０℃で４８時間加熱する以外は、実施例１と同様に行い、ＭＯＦ４を暗緑色の固体（８６ｍｇ）として得た。
[Example 4]
Using Cr(NO 3 ) 3.9H 2 O (188 mg, 0.472 mmol) as the metal salt, 24 mL of DMF and 1 mL of trifluoroacetic acid as the solvent, except heating at 90 °C for 72 hours and at 120 °C for 48 hours. The same procedure as in Example 1 was carried out to obtain MOF4 as a dark green solid (86 mg).
［実施例５］
有機配位子１（３０ｍｇ、０．０５５８ｍｍｏｌ）、金属塩としてＣｒ（ＯＡｃ）３（５４ｍｇ、０．２３５ｍｍｏｌ）、溶媒としてＤＭＦ１０ｍＬ及びトリフルオロ酢酸０．５ｍＬ用い、６０℃で７２時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ５を暗緑色の固体（２０ｍｇ）として得た。
[Example 5]
Organic ligand 1 (30 mg, 0.0558 mmol), Cr(OAc) 3 (54 mg, 0.235 mmol) as a metal salt, 10 mL of DMF and 0.5 mL of trifluoroacetic acid as a solvent, except for heat treatment at 60 ° C. for 72 hours. was carried out in the same manner as in Example 1 to obtain MOF5 as a dark green solid (20 mg).
［実施例６］
有機配位子１（１５０ｍｇ、０．３ｍｍｏｌ）、金属塩としてＣｒＣｌ３・６Ｈ２Ｏ（１６０ｍｇ、０．６ｍｍｏｌ）、ＤＭＦ３ｍＬを用い、オートクレーブ中、１９０℃で７２時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ６を青緑色の固体（９６ｍｇ）として得た。
[Example 6]
Example except that organic ligand 1 (150 mg, 0.3 mmol), CrCl 3 .6H 2 O (160 mg, 0.6 mmol) as a metal salt, and 3 mL of DMF were used and heat treated in an autoclave at 190° C. for 72 hours. The same procedure as in 1 was carried out to obtain MOF6 as a blue-green solid (96 mg).
［実施例７］
有機配位子１（６０ｍｇ、０．１１８ｍｍｏｌ）、金属塩としてＣｒＣｌ３・６Ｈ２Ｏ（６３ｍｇ、０．２３６ｍｍｏｌ）、ＤＭＦ２．４ｍＬを用い、９０℃で１４４時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ７を暗緑色の固体（６０ｍｇ）として得た。
[Example 7]
Example 1 except that organic ligand 1 (60 mg, 0.118 mmol), CrCl 3 .6H 2 O (63 mg, 0.236 mmol) as a metal salt, and 2.4 mL of DMF were used, and heat treatment was performed at 90° C. for 144 hours. In the same manner as above, MOF7 was obtained as a dark green solid (60 mg).
［実施例８］
有機配位子１（６０ｍｇ、０．１１８ｍｍｏｌ）、金属塩としてＣｒＣｌ３・６Ｈ２Ｏ（２４ｍｇ、０．０８８５ｍｍｏｌ）、ＤＭＦ３ｍＬを用い、オートクレーブ中、１９０℃で７２時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ８を青緑色の固体（２８ｍｇ）として得た。
[Example 8]
Example except that organic ligand 1 (60 mg, 0.118 mmol), CrCl 3 .6H 2 O (24 mg, 0.0885 mmol) as a metal salt, and 3 mL of DMF were used and heat-treated at 190° C. for 72 hours in an autoclave. The same procedure as in 1 was carried out to obtain MOF8 as a blue-green solid (28 mg).
［実施例９］
有機配位子１（６０ｍｇ、０．１１８ｍｍｏｌ）、金属塩としてＣｒＣｌ３・６Ｈ２Ｏ（４２ｍｇ、０．１５７ｍｍｏｌ）、ＤＭＦ４ｍＬを用い、オートクレーブ中、１９０℃で３６時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ９を青緑色の固体（７０ｍｇ）として得た。
[Example 9]
Example except that organic ligand 1 (60 mg, 0.118 mmol), CrCl 3 .6H 2 O (42 mg, 0.157 mmol) as a metal salt, and 4 mL of DMF were used and heat-treated at 190° C. for 36 hours in an autoclave. The same procedure as in 1 was carried out to obtain MOF9 as a blue-green solid (70 mg).
［実施例１０］
金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（１１０ｍｇ、０．４７２ｍｍｏｌ）を用い、９０℃で２４時間加熱処理する以外は、実施例１と同様に行い、ＭＯＦ１０を青色の固体（５４ｍｇ）として得た。
[Example 10]
The same procedure as in Example 1 was carried out except that Cu(NO 3 ) 2.3H 2 O (110 mg , 0.472 mmol) was used as the metal salt and heat treatment was performed at 90° C. for 24 hours, and MOF10 was converted into a blue solid (54 mg). obtained as.
［実施例１１］
金属塩Ｃｕ（ＯＡｃ）２・Ｈ２Ｏ（８６ｍｇ、０．４７２ｍｍｏｌ）のＤＭＦ１．２ｍＬの溶液を氷冷し、有機配位子１（６０ｍｍｇ、０．１１８ｍｍｏｌ）のＤＭＦ１．２ｍＬの溶液を静かに添加した。金属塩の溶液と有機配位子１の溶液は２層に分離した。得られた２層の溶液を０℃で２４時間静置した。固体が析出した溶液を実施例１と同様にして処理し、ＭＯＦ１１を青色の固体（６６ｍｇ）として得た。
[Example 11]
A solution of metal salt Cu(OAc) 2 ·H 2 O (86 mg, 0.472 mmol) in DMF 1.2 mL was cooled on ice, and a solution of organic ligand 1 (60 mmg, 0.118 mmol) in DMF 1.2 mL was gently added. Added. The metal salt solution and the organic ligand 1 solution were separated into two layers. The resulting two-layer solution was allowed to stand at 0° C. for 24 hours. The solution in which the solid precipitated was treated in the same manner as in Example 1 to obtain MOF11 as a blue solid (66 mg).
［実施例１２］
金属塩としてＦｅ（ＮＯ３）３・９Ｈ２Ｏ（１９１ｍｇ、０．４７２ｍｍｏｌ）をＤＭＦ２４ｍＬ及びトリフルオロ酢酸１ｍＬに溶解し、９０℃で７２時間、１２０℃で２４時間加熱処理する以外は実施例１と同様に行い、ＭＯＦ１２を赤橙色の固体（７４ｍｇ）として得た。
[Example 12]
Example 1 except that Fe(NO 3 ) 3.9H 2 O (191 mg, 0.472 mmol) as a metal salt was dissolved in 24 mL of DMF and 1 mL of trifluoroacetic acid, and heat treated at 90° C. for 72 hours and at 120° C. for 24 hours. In the same manner as above, MOF12 was obtained as a reddish-orange solid (74 mg).
［実施例１３］
金属塩としてＦｅ（ＮＯ３）３・９Ｈ２Ｏ（１９１ｍｇ、０．４７２ｍｍｏｌ）をＤＭＦ２４ｍＬに溶解し、９０℃で７２時間、加熱処理する以外は実施例１と同様に行い、ＭＯＦ１３を暗緑色の固体（７０ｍｇ）として得た。
[Example 13]
The same procedure as in Example 1 was carried out except that Fe(NO 3 ) 3.9H 2 O (191 mg , 0.472 mmol) as a metal salt was dissolved in 24 mL of DMF and heat treated at 90°C for 72 hours. Obtained as a solid (70mg).
［実施例１４］
金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１４０ｍｇ、０．４７２ｍｍｏｌ）、第２有機配位子として１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）（５３ｍｇ）をＤＭＦ９．４ｍＬに溶解し、６０℃で７２時間、加熱処理する以外は実施例１と同様に行い、ＭＯＦ１４を白色の固体（７１ｍｇ）として得た。
[Example 14]
Zn(NO 3 ) 2.6H 2 O (140 mg, 0.472 mmol) as a metal salt and 1,4-diazabicyclo[2.2.2]octane (DABCO) (53 mg) as a second organic ligand were added in DMF9. The same procedure as in Example 1 was performed except that the solution was dissolved in 4 mL and heat-treated at 60° C. for 72 hours, to obtain MOF14 as a white solid (71 mg).
［実施例１５］
金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１４０ｍｇ、０．４７２ｍｍｏｌ）、第２有機配位子として１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）（５３ｍｇ）をＤＭＦ１０ｍＬ及びトリフルオロ酢酸０．５ｍＬに溶解し、９０℃で７２時間、１２０℃で４８時間、加熱処理する以外は実施例１と同様に行い、ＭＯＦ１５を白色の固体（９４ｍｇ）として得た。
[Example 15]
Zn(NO 3 ) 2.6H 2 O (140 mg, 0.472 mmol) as a metal salt and 1,4-diazabicyclo[2.2.2]octane (DABCO) (53 mg) as a second organic ligand in 10 mL of DMF and The same procedure as in Example 1 was performed except that the solution was dissolved in 0.5 mL of trifluoroacetic acid and heated at 90° C. for 72 hours and at 120° C. for 48 hours, to obtain MOF15 as a white solid (94 mg).
［実施例１６］
金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（７０ｍｇ、０．２３５ｍｍｏｌ）、第２有機配位子として１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）（１３ｍｇ）をＤＭＦ４．７ｍＬに溶解し、オートクレーブ中１９０℃で２４時間、加熱処理する以外は実施例１と同様に行い、ＭＯＦ１６を白色の固体（７０ｍｇ）として得た。
[Example 16]
Zn(NO 3 ) 2.6H 2 O (70 mg, 0.235 mmol) as a metal salt and 1,4-diazabicyclo[2.2.2]octane (DABCO) (13 mg) as a second organic ligand were mixed in DMF4. The same procedure as in Example 1 was performed except that the solution was dissolved in 7 mL and heat-treated in an autoclave at 190° C. for 24 hours, to obtain MOF16 as a white solid (70 mg).
［実施例１７］
金属塩Ｚｎ（ＯＡｃ）２・２Ｈ２Ｏ（１０４ｍｇ、０．４７２ｍｍｏｌ）のＤＭＦ１．２ｍＬの溶液を氷冷し、有機配位子１（６０ｍｍｇ、０．１１８ｍｍｏｌ）のＤＭＦ１．２ｍＬの溶液を静かに添加した。金属塩の溶液と有機配位子１の溶液は２層に分離した。得られた２層の溶液を０℃で振盪した。得られた固体が析出した溶液を実施例１と同様にして処理し、ＭＯＦ１７を青色の固体（９０ｍｇ）として得た。
[Example 17]
A solution of metal salt Zn(OAc) 2.2H 2 O ( 104 mg, 0.472 mmol) in DMF 1.2 mL was cooled on ice, and a solution of organic ligand 1 (60 mmg, 0.118 mmol) in DMF 1.2 mL was gently added. Added. The metal salt solution and the organic ligand 1 solution were separated into two layers. The resulting two-layer solution was shaken at 0°C. The solution in which the obtained solid was precipitated was treated in the same manner as in Example 1 to obtain MOF17 as a blue solid (90 mg).
［実施例１８］
有機配位子１（１５０ｍｍｇ、０．３００ｍｍｏｌ）と金属塩としてのＺｒＣｌ４（１４０ｍｇ、０．６００ｍｍｏｌ）をＤＭＦ４ｍＬ、酢酸０．５ｍＬ及び水０．０６ｍＬに溶解し、１２０℃で２４時間加熱処理する以外は実施例１と同様に行い、ＭＯＦ１８を白色の固体（１８２ｍｇ）として得た。
[Example 18]
Organic ligand 1 (150 mmg, 0.300 mmol) and ZrCl 4 (140 mg, 0.600 mmol) as a metal salt are dissolved in 4 mL of DMF, 0.5 mL of acetic acid, and 0.06 mL of water, and heat treated at 120° C. for 24 hours. Except for this, the same procedure as in Example 1 was carried out to obtain MOF18 as a white solid (182 mg).
［実施例１９］
有機配位子１（５１ｍｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌＣｌ３・６Ｈ２Ｏ（９６ｍｇ、０．４ｍｍｏｌ）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１４０時間加熱する以外は実施例１と同様に行いＭＯＦ１９を白色の固体（７１ｍｇ）として得た。
[Example 19]
Organic ligand 1 (51 mmg, 0.1 mmol) and AlCl 3.6H 2 O (96 mg, 0.4 mmol) as a metal salt were dissolved in 10 mL of DMF, and after filtering with a membrane filter, the mixture was heated at 120 °C in a sealed vial at 140 °C. The same procedure as in Example 1 was carried out except for heating for a certain period of time, and MOF19 was obtained as a white solid (71 mg).
［実施例２０］
有機配位子１（５１ｍｍｇ、０．１ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１９ｍｇ、０．４ｍｍｏｌ）及び第２有機配位子として１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）（４５ｍｇ）をジエチルホルムアミド（ＤＥＦ）１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、６０℃で６７時間加熱処理する以外は実施例１と同様に行い、ＭＯＦ２０を白色の固体（７５ｍｇ）として得た。
[Example 20]
Organic ligand 1 (51 mmg, 0.1 mmol), Zn (NO 3 ) 2.6H 2 O (119 mg, 0.4 mmol) as the metal salt and 1,4-diazabicyclo[2.2 .2] Octane (DABCO) (45 mg) was dissolved in 10 mL of diethylformamide (DEF), filtered with a membrane filter, and then heated in a sealed vial at 60° C. for 67 hours, but in the same manner as in Example 1. MOF20 was obtained as a white solid (75 mg).
［実施例２１］
有機配位子１（５１ｍｍｇ、０．１ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１９ｍｇ、０．４ｍｍｏｌ）及び第２有機配位子として１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）（１１ｍｇ）をジエチルホルムアミド（ＤＥＦ）５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１９０℃で６７時間加熱処理する以外は実施例１と同様に行い、ＭＯＦ２１を白色の固体（７０ｍｇ）として得た。
[Example 21]
Organic ligand 1 (51 mmg, 0.1 mmol), Zn (NO 3 ) 2.6H 2 O (119 mg, 0.4 mmol) as the metal salt and 1,4-diazabicyclo[2.2 .2] Octane (DABCO) (11 mg) was dissolved in 5 mL of diethylformamide (DEF), filtered with a membrane filter, and then heated in a sealed vial at 190° C. for 67 hours, but in the same manner as in Example 1. MOF21 was obtained as a white solid (70mg).
実施例１～２１で得られた金属有機構造体について、以下の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２に示す。
（ＢＥＴ比表面積測定及び水素貯蔵量測定）
ＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量の測定は、ガス吸着量測定装置Ｔｒｉｓｔａｒ－ＩＩ（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を用いて行った。
ＢＥＴ比表面積は次の方法で算出した。金属有機構造体の５０ｍｇ程度を、ガラスセルの内部に入れた。ガラスセルの内部は１３５℃の温度で真空まで減圧し、６時間乾燥させた。ガラスセルをガス吸着量測定装置に装着し、液体窒素入りの恒温槽に浸漬した。ガラスセルに含有される窒素の圧力を徐々に増加させた。ガラスセルの内部に導入された窒素の圧力が１．０×１０５Ｐａとなるまで測定を行った。
７７Ｋ常圧での水素貯蔵量は次の方法で算出した。窒素の測定後、水素へとガス種を変更し測定を行った。ガラスセルに含有される水素の圧力を徐々に増加させた。ガラスセルの内部に導入された水素の圧力が１．０×１０５Ｐａとなるまで測定を行った。
Regarding the metal-organic structures obtained in Examples 1 to 21, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured by the following method. The results are shown in Table 2.
(BET specific surface area measurement and hydrogen storage amount measurement)
The BET specific surface area and the hydrogen storage amount at 77 K and atmospheric pressure were measured using a gas adsorption measurement device Tristar-II (manufactured by Micromeritics).
The BET specific surface area was calculated by the following method. Approximately 50 mg of the metal-organic framework was placed inside the glass cell. The inside of the glass cell was evacuated to 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 constant temperature bath containing liquid nitrogen. The pressure of nitrogen contained in the glass cell was gradually increased. Measurement was performed until the pressure of nitrogen introduced into the glass cell reached 1.0×10 5 Pa.
The hydrogen storage amount at 77K normal pressure was calculated by the following method. After measuring nitrogen, the gas type was changed to hydrogen and measurements were taken. The pressure of hydrogen contained in the glass cell was gradually increased. Measurement was performed until the pressure of hydrogen introduced into the glass cell reached 1.0×10 5 Pa.
［実施例２２］
有機配位子２（４０ｍｍｇ、０．０６４８ｍｍｏｌ）と金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（１３１ｍｇ、０．５４２ｍｍｏｌ）のＤＭＦ２．１ｍＬ溶液を密閉したバイアル中、１５０℃で２時間加熱する以外は、実施例１と同様に行い、ＭＯＦ２２を青色の固体（３１ｍｇ）として得た。
[Example 22]
A 2.1 mL DMF solution of organic ligand 2 (40 mmg, 0.0648 mmol) and metal salt Cu(NO 3 ) 2.3H 2 O (131 mg, 0.542 mmol) was heated at 150° C. for 2 hours in a sealed vial. The same procedure as in Example 1 was carried out except that MOF22 was obtained as a blue solid (31 mg).
［実施例２３］
有機配位子２（４１ｍｍｇ、０．０６５６ｍｍｏｌ）と金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（９６ｍｇ、０．３９２ｍｍｏｌ）のＤＭＡ３．９ｍＬ溶液を密閉したバイアル中、１１５℃で２４時間加熱する以外は、実施例１と同様に行い、ＭＯＦ２３を青色の固体（２６ｍｇ）として得た。
[Example 23]
A 3.9 mL DMA solution of organic ligand 2 (41 mmg, 0.0656 mmol) and metal salt Cu(NO 3 ) 2.3H 2 O (96 mg, 0.392 mmol) was heated at 115° C. for 24 hours in a sealed vial. The same procedure as in Example 1 was carried out except that MOF23 was obtained as a blue solid (26 mg).
［実施例２４］
ＤＭＡ０．６５ｍＬ用い、９０℃で加熱する以外は、実施例２３と同様に行いＭＯＦ２４を青色の固体（２１ｍｇ）として得た。
[Example 24]
The same procedure as in Example 23 was performed except that 0.65 mL of DMA was used and heating was performed at 90° C. to obtain MOF24 as a blue solid (21 mg).
［実施例２５］
金属塩としてＭｎＣｌ２・４Ｈ２Ｏ（６７ｍｇ、０．３４１ｍｍｏｌ）を用い、溶媒としてＤＭＦ１．３ｍＬを用い、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で２４時間加熱する以外は実施例２２と同様に行い、ＭＯＦ２５をピンク色の固体（２４ｍｇ）として得た。
[Example 25]
Example 22 except that MnCl 2 .4H 2 O (67 mg, 0.341 mmol) was used as the metal salt, 1.3 mL of DMF was used as the solvent, and after filtration with a membrane filter, heating was performed at 120° C. for 24 hours in a sealed vial. In the same manner as above, MOF25 was obtained as a pink solid (24 mg).
［実施例２６］
金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１５４ｍｇ、０．５１８ｍｍｏｌ）を用い、溶媒としてＤＭＦ１．７ｍＬを用い、メンブランフィルターでろ過後、密閉したバイアル中、１５０℃で３時間加熱する以外は実施例２２と同様に行い、ＭＯＦ２６を淡黄色の固体（２７ｍｇ）として得た。
[Example 26]
Other than using Zn(NO 3 ) 2.6H 2 O (154 mg, 0.518 mmol) as the metal salt and 1.7 mL of DMF as the solvent, heating at 150 ° C. for 3 hours in a sealed vial after filtration with a membrane filter. was carried out in the same manner as in Example 22 to obtain MOF26 as a pale yellow solid (27 mg).
［実施例２７］
有機配位子２（２０ｍｇ、０．０３２３ｍｍｏｌ）、第２有機配位子として４，４’ －ビピリジル（２０ｍｇ、０．１３１ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（４８ｍｇ、０．１０１ｍｍｏｌ）のＤＭＦ０．３３ｍＬ溶液を、密閉したバイアル中、７０℃で９６時間加熱する以外は実施例１と同様に行い、ＭＯＦ２７を白色の固体（１０ｍｇ）として得た。
[Example 27]
Organic ligand 2 (20 mg, 0.0323 mmol), 4,4'-bipyridyl (20 mg, 0.131 mmol) as the second organic ligand, Zn(NO 3 ) 2.6H 2 O (48 mg, The same procedure as in Example 1 was performed except that a solution of 0.101 mmol) in 0.33 mL of DMF was heated at 70° C. for 96 hours in a sealed vial to obtain MOF27 as a white solid (10 mg).
［実施例２８］
有機配位子２（５９ｍｇ、０．０９５４ｍｍｏｌ）、金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１４１ｍｇ、０．３７６ｍｍｏｌ）のＤＭＦ８．１ｍＬ溶液を、密閉したバイアル中、１２０℃で７２時間加熱する以外は実施例１と同様に行い、ＭＯＦ２８を黄色の固体（３１ｍｇ）として得た。
[Example 28]
A solution of organic ligand 2 (59 mg, 0.0954 mmol) and Al(NO 3 ) 3.9H 2 O ( 141 mg, 0.376 mmol) as the metal salt in 8.1 mL of DMF was heated at 120° C. for 72 hours in a sealed vial. The same procedure as in Example 1 was performed except for heating, and MOF28 was obtained as a yellow solid (31 mg).
［実施例２９］
有機配位子２（４０ｍｇ、０．０６４７ｍｍｏｌ）、金属塩としてＺｒＣｌ４（７６ｍｇ、０．３２６ｍｍｏｌ）、添加剤として安息香酸（３９７ｍｇ、３．２５ｍｍｏｌ）のＤＭＦ８．１ｍＬ溶液を、密閉したバイアル中、９０℃で１４４時間、１２０℃で２１６時間加熱する以外は実施例１と同様に行い、ＭＯＦ２９を白色の固体（４２ｍｇ）として得た。
[Example 29]
A DMF 8.1 mL solution of organic ligand 2 (40 mg, 0.0647 mmol), ZrCl 4 (76 mg, 0.326 mmol) as a metal salt, and benzoic acid (397 mg, 3.25 mmol) as an additive was added in a sealed vial. The same procedure as in Example 1 was performed except that heating was performed at 90° C. for 144 hours and at 120° C. for 216 hours, to obtain MOF29 as a white solid (42 mg).
実施例２２～２９で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表３に示す。 Regarding the metal-organic structures obtained in Examples 22 to 29, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 3.
［実施例３０］
有機配位子３（４１ｍｍｇ、０．０６９８ｍｍｏｌ）と金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（１２２ｍｇ、０．５０５ｍｍｏｌ）のＤＭＡ６．８ｍＬ溶液を、密閉したバイアル中、９０℃で４時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３０を青色の固体（２７ｍｇ）として得た。
[Example 30]
A 6.8 mL solution of organic ligand 3 (41 mmg, 0.0698 mmol) and Cu(NO 3 ) 2.3H 2 O as metal salt (122 mg, 0.505 mmol) in DMA was added in a sealed vial at 90° C. for 4 hours. The same procedure as in Example 1 was performed except for heating, and MOF30 was obtained as a blue solid (27 mg).
［実施例３１］
１２０℃で４時間加熱する以外は、実施例３０と同様に行い、ＭＯＦ３１を青色の固体（３０ｍｇ）として得た。
[Example 31]
The same procedure as Example 30 was carried out except that heating was performed at 120° C. for 4 hours, and MOF31 was obtained as a blue solid (30 mg).
［実施例３２］
有機配位子３（３０ｍｍｇ、０．０５１１ｍｍｏｌ）と金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１２１ｍｇ、０．４０８ｍｍｏｌ）を、ＤＭＦ５．１ｍＬに溶解し、メンブレンフィルターでろ過後、密閉したバイアル中、１２０℃で４８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３２を白色の固体（２０ｍｇ）として得た。
[Example 32]
Organic ligand 3 (30 mmg, 0.0511 mmol) and Zn(NO 3 ) 2.6H 2 O (121 mg, 0.408 mmol) as a metal salt were dissolved in 5.1 mL of DMF, filtered with a membrane filter, and then sealed. The same procedure as in Example 1 was carried out except that the mixture was heated at 120° C. for 48 hours in a vial to obtain MOF32 as a white solid (20 mg).
［実施例３３］
有機配位子３（２１ｍｍｇ、０．０３６０ｍｍｏｌ）と金属塩としてＺｒＣｌ４（４０ｍｇ、０．１７１ｍｍｏｌ）を、ＤＭＦ６ｍＬに溶解し、メンブレンフィルターでろ過後、密閉したバイアル中、９０℃で２４時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３３を白色の固体（６０ｍｇ）として得た。
[Example 33]
Organic ligand 3 (21 mmg, 0.0360 mmol) and ZrCl 4 (40 mg, 0.171 mmol) as a metal salt were dissolved in 6 mL of DMF, filtered through a membrane filter, and then heated at 90 °C for 24 hours in a sealed vial. Except for this, the same procedure as in Example 1 was carried out to obtain MOF33 as a white solid (60 mg).
実施例３０～３３で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表４に示す。 Regarding the metal-organic structures obtained in Examples 30 to 33, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 4.
［実施例３４］
有機配位子４（４０ｍｇ、０．０６１９ｍｍｏｌ）、金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（７５ｍｇ、０．３１０ｍｍｏｌ）のＤＭＡ１．２４ｍＬの溶液を、密閉したバイアル中、１２０℃で４８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３４を青色の固体（３４ｍｇ）として得た。
[Example 34]
A solution of organic ligand 4 (40 mg, 0.0619 mmol), Cu(NO 3 ) 2.3H 2 O (75 mg, 0.310 mmol) as metal salt in 1.24 mL of DMA was heated at 120° C. for 48 hours in a sealed vial. The same procedure as in Example 1 was carried out except that heating was performed for a certain period of time, and MOF34 was obtained as a blue solid (34 mg).
［実施例３５］
有機配位子４（５０ｍｇ、０．０７７３ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１７ｍｇ、０．３９３ｍｍｏｌ）、第２有機配位子としてＤＡＢＣＯ（３７ｍｇ、０．３２７ｍｍｏｌ）のＤＭＡ１．８５ｍＬの溶液を、密閉したバイアル中、１２０℃で７２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３５を白色の固体（４７ｍｇ）として得た。
[Example 35]
Organic ligand 4 (50 mg, 0.0773 mmol), Zn(NO 3 ) 2.6H 2 O (117 mg, 0.393 mmol) as a metal salt, and DABCO (37 mg, 0.327 mmol) as a second organic ligand. The same procedure as in Example 1 was performed except that a solution of 1.85 mL of DMA was heated at 120° C. for 72 hours in a sealed vial to obtain MOF35 as a white solid (47 mg).
［実施例３６］
有機配位子４（５０ｍｇ、０．０７７３ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１７ｍｇ、０．３８７ｍｍｏｌ）、第２有機配位子として４，４‘-ビピリジル（１９ｍｇ、０．１２４ｍｍｏｌ）のＤＭＡ１．７５ｍＬの溶液を、密閉したバイアル中、１２０℃で７２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３６を白色の固体（１７ｍｇ）として得た。
[Example 36]
Organic ligand 4 (50 mg, 0.0773 mmol), Zn( NO3 ) 2.6H2O (117 mg, 0.387 mmol) as a metal salt, 4,4'-bipyridyl (19 mg, Example 1 was repeated, except that a solution of 1.75 mL of DMA (0.124 mmol) was heated at 120° C. for 72 hours in a sealed vial to obtain MOF36 as a white solid (17 mg).
［実施例３７］
有機配位子４（４０ｍｇ、０．０６１９ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（９２ｍｇ、０．３０９ｍｍｏｌ）、第２有機配位子として１，２－ジ（４－ピリジル）エテン（５７ｍｇ、０．３１１ｍｍｏｌ）のＤＭＡ１．２５ｍＬの溶液を、密閉したバイアル中、１２０℃で２２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３７を白色の固体（２０ｍｇ）として得た。
[Example 37]
Organic ligand 4 (40 mg, 0.0619 mmol), Zn(NO 3 ) 2.6H 2 O (92 mg, 0.309 mmol) as the metal salt, 1,2-di(4-pyridyl) as the second organic ligand. ) Example 1 was repeated except that a solution of ethene (57 mg, 0.311 mmol) in 1.25 mL of DMA was heated at 120 °C for 22 hours in a sealed vial to obtain MOF37 as a white solid (20 mg). Ta.
［実施例３８］
有機配位子４（４０ｍｇ、０．０６１９ｍｍｏｌ）、金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（９２ｍｇ、０．３０９ｍｍｏｌ）、第２有機配位子として１，２－ジ（４－ピリジル）エタン（５７ｍｇ、０．３１３ｍｍｏｌ）のＤＭＡ１．２５ｍＬの溶液を、密閉したバイアル中、１２０℃で２２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３８を白色の固体（３３ｍｇ）として得た。
[Example 38]
Organic ligand 4 (40 mg, 0.0619 mmol), Zn(NO 3 ) 2.6H 2 O (92 mg, 0.309 mmol) as the metal salt, 1,2-di(4-pyridyl) as the second organic ligand. ) Example 1 was repeated except that a solution of ethane (57 mg, 0.313 mmol) in 1.25 mL of DMA was heated at 120 °C for 22 h in a sealed vial to obtain MOF38 as a white solid (33 mg). Ta.
実施例３４～３８で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表５に示す。 Regarding the metal-organic structures obtained in Examples 34 to 38, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 5.
［実施例３９］
有機配位子５（３１ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（３１ｍｇ、０．２ｍｍｏｌ、有機配位子５のカルボン酸残基と当量）をＤＭＦ１ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ３９を白色の固体（３０ｍｇ）として得た。
[Example 39]
Organic ligand 5 (31 mg, 0.05 mmol) and Zn(NO 3 ) 2.6H 2 O as a metal salt (31 mg, 0.2 mmol, equivalent to the carboxylic acid residue of organic ligand 5) were dissolved in 1 mL of DMF. The same procedure as in Example 1 was carried out, except that after filtration with a membrane filter, the mixture was heated at 120° C. for 48 hours in a sealed vial to obtain MOF39 as a white solid (30 mg).
［実施例４０］
金属塩としてＺｎ（ＯＡｃ）２・２Ｈ２Ｏ（８８ｍｇ、０．４ｍｍｏｌ）のＤＭＦ１ｍＬ溶液に有機配位子５（６２ｍｇ、０．１ｍｍｏｌ）の１ｍＬＤＭＦ溶液を添加し、密閉したバイアル中、９０℃で２４時間、１２０℃で９６時間加熱した以外は、実施例１と同様に行い、ＭＯＦ４０を白色の固体（４０ｍｇ）として得た。
[Example 40]
A 1 mL DMF solution of organic ligand 5 (62 mg, 0.1 mmol) was added to a 1 mL DMF solution of Zn(OAc) 2.2H 2 O (88 mg, 0.4 mmol) as a metal salt, and the mixture was heated at 90 °C in a sealed vial. The same procedure as in Example 1 was performed except that the mixture was heated at 120° C. for 24 hours and 96 hours to obtain MOF40 as a white solid (40 mg).
［実施例４１］
有機配位子５（６２ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ）をＤＭＦ２ｍＬ及びトリフルオロ酢酸０．０２ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、７０℃で９６時間加熱した以外は、実施例１と同様に行い、ＭＯＦ４１を白色の固体（１０ｍｇ）として得た。
[Example 41]
Organic ligand 5 (62 mg, 0.1 mmol) and metal salt Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol) were dissolved in 2 mL of DMF and 0.02 mL of trifluoroacetic acid, and filtered with a membrane filter. Thereafter, the same procedure as in Example 1 was performed except that the mixture was heated at 70° C. for 96 hours in a sealed vial to obtain MOF41 as a white solid (10 mg).
［実施例４２］
金属塩としてＦｅ（ＮＯ３）３・９Ｈ２Ｏ（１６２ｍｇ、０．４ｍｍｏｌ）を用いる以外は、実施例４１と同様に行い、ＭＯＦ４２を赤色の固体（１０ｍｇ）として得た。
[Example 42]
The same procedure as Example 41 was performed except that Fe(NO 3 ) 3 ·9H 2 O (162 mg, 0.4 mmol) was used as the metal salt, and MOF42 was obtained as a red solid (10 mg).
実施例３９～４２で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表６に示す。 Regarding the metal-organic structures obtained in Examples 39 to 42, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 6.
［実施例４３］
有機配位子６（５９ｍｇ、０．１ｍｍｏｌ）を用いる以外は、実施例４１と同様に行い、ＭＯＦ４３を白色の固体（１０ｍｇ）として得た。
[Example 43]
The same procedure as Example 41 was performed except that organic ligand 6 (59 mg, 0.1 mmol) was used to obtain MOF43 as a white solid (10 mg).
［実施例４４］
有機配位子６（２９ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（４８ｍｇ、０．２ｍｍｏｌ）をＤＭＡ１ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ４４を青色の固体（３０ｍｇ）として得た。
[Example 44]
Organic ligand 6 (29 mg, 0.05 mmol) and Cu(NO 3 ) 2.3H 2 O ( 48 mg, 0.2 mmol) as a metal salt were dissolved in 1 mL of DMA, and after filtering with a membrane filter, in a sealed vial. The same procedure as in Example 1 was performed except that heating was performed at 120° C. for 48 hours, and MOF44 was obtained as a blue solid (30 mg).
［実施例４５］
溶媒としてＤＭＡ１ｍＬに硝酸０．０２ｍＬをさらに添加した以外は、実施例４４と同様に行い、ＭＯＦ４５を青色の固体（２５ｍｇ）として得た。
[Example 45]
The same procedure as Example 44 was performed except that 0.02 mL of nitric acid was further added to 1 mL of DMA as a solvent, and MOF45 was obtained as a blue solid (25 mg).
［実施例４６］
有機配位子６（５９ｍｇ、０．１ｍｍｏｌ）を用いる以外は、実施例４２と同様に行い、ＭＯＦ４６を赤色の固体（２０ｍｇ）として得た。
[Example 46]
The same procedure as Example 42 was performed except that organic ligand 6 (59 mg, 0.1 mmol) was used to obtain MOF46 as a red solid (20 mg).
実施例４３～４６で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表７に示す。 Regarding the metal-organic structures obtained in Examples 43 to 46, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 7.
［実施例４７］
有機配位子７（６４ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子７中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ４７を白色の固体（８９ｍｇ）として得た。
[Example 47]
Organic ligand 7 (64 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 7) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 48 hours in a sealed vial to obtain MOF47 as a white solid (89 mg).
［実施例４８］
有機配位子８（６０ｍｇ、１ｍｍｏｌ）を用いる以外、実施例４７と同様に行い、ＭＯＦ４８を白色の固体（８９ｍｇ）を得た。
[Example 48]
The same procedure as Example 47 was carried out except that organic ligand 8 (60 mg, 1 mmol) was used to obtain MOF48 as a white solid (89 mg).
［実施例４９］
金属塩としてＺｒＣｌ４（９３ｍｇ）を用い、さらに溶媒としてＤＭＦ１０ｍＬに酢酸０．５ｍＬを添加する以外、実施例４８と同様に行い、ＭＯＦ４９を白色の固体（６９ｍｇ）として得た。
[Example 49]
The same procedure as in Example 48 was performed except that ZrCl 4 (93 mg) was used as the metal salt and 0.5 mL of acetic acid was added to 10 mL of DMF as a solvent to obtain MOF49 as a white solid (69 mg).
［実施例５０］
有機配位子９（６４ｍｇ、０．１ｍｍｏｌ）を用いる以外、実施例４７と同様に行い、ＭＯＦ５０を白色の固体（５２ｍｇ）として得た。
[Example 50]
The same procedure as Example 47 was carried out except that organic ligand 9 (64 mg, 0.1 mmol) was used to obtain MOF50 as a white solid (52 mg).
実施例４７～５０で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表８に示す。 Regarding the metal-organic structures obtained in Examples 47 to 50, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 8.
［実施例５１］
有機配位子１０（６１ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９２時間加熱処理する以外は、実施例４７と同様に行い、ＭＯＦ５１を白色の固体（３８ｍｇ）として得た。
[Example 51]
The same procedure as in Example 47 was performed except that organic ligand 10 (61 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 92 hours, to obtain MOF51 as a white solid (38 mg).
［実施例５２］
金属塩としてＣｕ（ＮＯ３）２・３Ｈ２Ｏ（９７ｍｇ、０．４ｍｍｏｌ）を用い、溶媒としてＤＭＡを用いる以外は、実施例５１と同様に行い、ＭＯＦ５２を青色の固体（５４ｍｇ）を得た。
[Example 52]
The same procedure as Example 51 was performed except that Cu(NO 3 ) 2.3H 2 O (97 mg, 0.4 mmol) was used as the metal salt and DMA was used as the solvent, and MOF52 was obtained as a blue solid (54 mg). .
［実施例５３］
金属塩としてＦｅ（ＮＯ３）３・９Ｈ２Ｏ（１６１ｍｇ、０．４ｍｍｏｌ）を用い、１２０℃で４３時間加熱処理する以外、実施例５１と同等に行い、ＭＯＦ５３を濃赤色の固体（６１ｍｇ）を得た。
[Example 53]
The same procedure as Example 51 was carried out except that Fe( NO 3 ) 3.9H 2 O (161 mg, 0.4 mmol) was used as the metal salt and heat treatment was performed at 120° C. for 43 hours, and MOF53 was converted into a dark red solid (61 mg). I got it.
［実施例５４］
金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１９ｍｇ、０．４ｍｍｏｌ）を用いる以外、実施例５１と同等に行い、ＭＯＦ５４を白色の固体（７３ｍｇ）を得た。
[Example 54]
The same procedure as in Example 51 was performed except that Zn(NO 3 ) 2.6H 2 O (119 mg, 0.4 mmol) was used as the metal salt, and MOF54 was obtained as a white solid (73 mg).
［実施例５５］
金属塩としてＺｒＣｌ４（９３ｍｇ、０．４ｍｍｏｌ）を用い、さらに溶媒としてＤＭＦ１０ｍＬに酢酸０．５ｍＬを添加する以外、実施例５１と同等に行い、ＭＯＦ５５を白色の固体（８１ｍｇ）として得た。
[Example 55]
The same procedure as in Example 51 was performed except that ZrCl 4 (93 mg, 0.4 mmol) was used as the metal salt and 0.5 mL of acetic acid was added to 10 mL of DMF as a solvent to obtain MOF55 as a white solid (81 mg).
［実施例５６］
有機配位子１０（６１ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子１０中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及びギ酸１ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４３時間加熱した以外は、実施例１と同様に行い、ＭＯＦ５６を白色の固体（８４ｍｇ）として得た。
[Example 56]
Organic ligand 10 (61 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 10) as a metal salt were added in 10 mL of DMF and MOF56 was obtained as a white solid (84 mg) in the same manner as in Example 1, except that it was dissolved in 1 ml of formic acid, filtered through a membrane filter, and then heated at 120° C. for 43 hours in a sealed vial.
実施例５１～５６で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表９に示す。 Regarding the metal-organic structures obtained in Examples 51 to 56, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 9.
［実施例５７］
有機配位子１１（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ５７を白色の固体（１１８ｍｇ）として得た。
[Example 57]
The same procedure as in Example 51 was performed except that organic ligand 11 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF57 as a white solid (118 mg).
［実施例５８］
有機配位子１１（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ５８を濃赤色の固体（１００ｍｇ）として得た。
[Example 58]
The same procedure as in Example 53 was performed except that organic ligand 11 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF58 as a deep red solid (100 mg).
［実施例５９］
有機配位子１１（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ５９を白色の固体（５０ｍｇ）として得た。
[Example 59]
The same procedure as in Example 54 was performed except that organic ligand 11 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF59 as a white solid (50 mg).
［実施例６０］
有機配位子１１（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ６０を白色の固体（１１６ｍｇ）として得た。
[Example 60]
MOF60 was obtained as a white solid (116 mg) in the same manner as in Example 55, except that organic ligand 11 (64 mg, 0.1 mmol) was used and heat treated at 120° C. for 42 hours.
実施例５７～６０で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１０に示す。 Regarding the metal-organic structures obtained in Examples 57 to 60, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 10.
［実施例６１］
有機配位子１２（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ６１を白色の固体（９４ｍｇ）として得た。
[Example 61]
The same procedure as in Example 51 was performed except that organic ligand 12 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 92 hours to obtain MOF61 as a white solid (94 mg).
［実施例６２］
有機配位子１２（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９２時間加熱処理する以外、実施例５２と同様に行い、ＭＯＦ６２を青色の固体（５６ｍｇ）として得た。
[Example 62]
The same procedure as in Example 52 was performed except that organic ligand 12 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 92 hours to obtain MOF62 as a blue solid (56 mg).
［実施例６３］
有機配位子１２（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ６３を濃赤色の固体（４８ｍｇ）として得た。
[Example 63]
The same procedure as in Example 53 was performed except that organic ligand 12 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF63 as a deep red solid (48 mg).
［実施例６４］
有機配位子１２（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９１時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ６４を白色の固体（１０３ｍｇ）として得た。
[Example 64]
The same procedure as in Example 54 was performed except that organic ligand 12 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 91 hours, to obtain MOF64 as a white solid (103 mg).
［実施例６５］
有機配位子１２（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９０時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ６５を白色の固体（１０３ｍｇ）として得た。
[Example 65]
The same procedure as in Example 55 was performed except that organic ligand 12 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 90 hours to obtain MOF65 as a white solid (103 mg).
実施例６１～６５で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１１に示す。 Regarding the metal-organic structures obtained in Examples 61 to 65, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 11.
［実施例６６］
有機配位子１３（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ６６を白色の固体（８３ｍｇ）として得た。
[Example 66]
The same procedure as in Example 51 was performed except that organic ligand 13 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF66 as a white solid (83 mg).
［実施例６７］
有機配位子１３（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で１１７時間加熱処理する以外、実施例５２と同様に行い、ＭＯＦ６７を青色の固体（９７ｍｇ）として得た。
[Example 67]
The same procedure as in Example 52 was performed except that organic ligand 13 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 117 hours to obtain MOF67 as a blue solid (97 mg).
［実施例６８］
有機配位子１３（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ６８を濃赤色の固体（９４ｍｇ）として得た。
[Example 68]
The same procedure as in Example 53 was performed except that organic ligand 13 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF68 as a deep red solid (94 mg).
［実施例６９］
有機配位子１３（６４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で１０６時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ６９を白色の固体（１５７ｍｇ）として得た。
[Example 69]
The same procedure as in Example 54 was performed except that organic ligand 13 (64 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 106 hours, to obtain MOF69 as a white solid (157 mg).
［実施例７０］
有機配位子１３（６５ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子１３中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及びギ酸１ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１５時間加熱した以外は、実施例１と同様に行い、ＭＯＦ７０を白色の固体（７８ｍｇ）として得た。
[Example 70]
Organic ligand 13 (65 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 13) as a metal salt were mixed in 10 mL of DMF and MOF70 was obtained as a white solid (78 mg) in the same manner as in Example 1, except that it was dissolved in 1 ml of formic acid, filtered through a membrane filter, and heated at 120° C. for 115 hours in a sealed vial.
［実施例７１］
有機配位子１３（６５ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子１３中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び濃塩酸０．０５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ７１を白色の固体（１５．３ｍｇ）として得た。
[Example 71]
Organic ligand 13 (65 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 13) as a metal salt were mixed in 10 mL of DMF and MOF71 was obtained as a white solid (15.3 mg) in the same manner as in Example 1, except that it was dissolved in 0.05 ml of concentrated hydrochloric acid, filtered through a membrane filter, and heated at 120°C for 68 hours in a sealed vial. Ta.
実施例６６～７１で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１２に示す。 Regarding the metal-organic structures obtained in Examples 66 to 71, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 12.
［実施例７２］
有機配位子１４（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ７２を白色の固体（４９ｍｇ）として得た。
[Example 72]
The same procedure as in Example 51 was performed except that organic ligand 14 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF72 as a white solid (49 mg).
［実施例７３］
有機配位子１４（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ７３を濃赤色の固体（１００ｍｇ）として得た。
[Example 73]
The same procedure as in Example 53 was performed except that organic ligand 14 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF73 as a deep red solid (100 mg).
［実施例７４］
有機配位子１４（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で１０５時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ７４を白色の固体（１１８ｍｇ）として得た。
[Example 74]
The same procedure as in Example 54 was performed except that organic ligand 14 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 105 hours to obtain MOF74 as a white solid (118 mg).
［実施例７５］
有機配位子１４（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９０時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ７５を白色の固体（１１６ｍｇ）として得た。
[Example 75]
The same procedure as in Example 55 was performed except that organic ligand 14 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 90 hours to obtain MOF75 as a white solid (116 mg).
［実施例７６］
有機配位子１４（６７ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子１４中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び濃塩酸０．０５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ７６を白色の固体（２５ｍｇ）として得た。
[Example 76]
Organic ligand 14 (67 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 14) as a metal salt were mixed in 10 mL of DMF and The same procedure as in Example 1 was performed except that the solution was dissolved in 0.05 ml of concentrated hydrochloric acid, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF76 as a white solid (25 mg).
実施例７２～７６で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１３に示す。 Regarding the metal-organic structures obtained in Examples 72 to 76, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 13.
［実施例７７］
有機配位子１５（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ７７を白色の固体（５２ｍｇ）として得た。
[Example 77]
The same procedure as in Example 51 was performed except that organic ligand 15 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF77 as a white solid (52 mg).
［実施例７８］
有機配位子１５（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ７８を濃赤色の固体（７５ｍｇ）として得た。
[Example 78]
The same procedure as in Example 53 was performed except that organic ligand 15 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF78 as a deep red solid (75 mg).
［実施例７９］
有機配位子１５（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ７９を白色の固体（５２ｍｇ）として得た。
[Example 79]
The same procedure as in Example 54 was performed except that organic ligand 15 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF79 as a white solid (52 mg).
［実施例８０］
有機配位子１５（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ８０を白色の固体（１２８ｍｇ）として得た。
[Example 80]
The same procedure as in Example 55 was performed except that organic ligand 15 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF80 as a white solid (128 mg).
実施例７７～８０で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１４に示す。 Regarding the metal-organic structures obtained in Examples 77 to 80, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 14.
［実施例８１］
有機配位子１６（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ８１をオレンジ色の固体（１０ｍｇ）として得た。
[Example 81]
The same procedure as in Example 51 was performed except that organic ligand 16 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF81 as an orange solid (10 mg).
［実施例８２］
有機配位子１６（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９１時間加熱処理する以外、実施例５２と同様に行い、ＭＯＦ８２を青緑色の固体（１２ｍｇ）として得た。
[Example 82]
The same procedure as in Example 52 was performed except that organic ligand 16 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 91 hours, to obtain MOF82 as a blue-green solid (12 mg).
［実施例８３］
有機配位子１６（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ８３をオレンジ色の固体（１０ｍｇ）として得た。
[Example 83]
The same procedure as in Example 53 was performed except that organic ligand 16 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF83 as an orange solid (10 mg).
［実施例８４］
有機配位子１６（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４２時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ８４を淡黄色の固体（６８ｍｇ）として得た。
[Example 84]
The same procedure as in Example 54 was performed except that organic ligand 16 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 42 hours to obtain MOF84 as a pale yellow solid (68 mg).
［実施例８５］
有機配位子１６（７０ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９１時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ８５を白色の固体（１０２ｍｇ）として得た。
[Example 85]
The same procedure as in Example 55 was performed except that organic ligand 16 (70 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 91 hours, to obtain MOF85 as a white solid (102 mg).
実施例８１～８５で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１５に示す。 Regarding the metal-organic structures obtained in Examples 81 to 85, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 15.
［実施例８６］
有機配位子１７（３４ｍｇ、０．０５ｍｍｏｌ）を用い、１２０℃で４４時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ８６を淡黄色の固体（８ｍｇ）として得た。
[Example 86]
The same procedure as in Example 51 was performed except that organic ligand 17 (34 mg, 0.05 mmol) was used and heat treatment was performed at 120° C. for 44 hours, to obtain MOF86 as a pale yellow solid (8 mg).
［実施例８７］
有機配位子１７（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９１時間加熱処理する以外、実施例５２と同様に行い、ＭＯＦ８７を青色の固体（５２ｍｇ）として得た。
[Example 87]
The same procedure as in Example 52 was performed except that organic ligand 17 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 91 hours, to obtain MOF87 as a blue solid (52 mg).
［実施例８８］
有機配位子１７（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４４時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ８８を茶色の固体（８５ｍｇ）として得た。
[Example 88]
The same procedure as in Example 53 was performed except that organic ligand 17 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 44 hours to obtain MOF88 as a brown solid (85 mg).
［実施例８９］
有機配位子１７（３４ｍｇ、０．０５ｍｍｏｌ）を用い、１２０℃で４４時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ８９を白色の固体（３３ｍｇ）として得た。
[Example 89]
The same procedure as in Example 54 was performed except that organic ligand 17 (34 mg, 0.05 mmol) was used and heat treatment was performed at 120° C. for 44 hours to obtain MOF89 as a white solid (33 mg).
［実施例９０］
有機配位子１７（６７ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９１時間加熱処理する以外、実施例５５と同様に行い、ＭＯＦ９０を白色の固体（９９ｍｇ）として得た。
[Example 90]
The same procedure as in Example 55 was performed except that organic ligand 17 (67 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 91 hours, to obtain MOF90 as a white solid (99 mg).
実施例８６～９０で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１６に示す。 Regarding the metal-organic structures obtained in Examples 86 to 90, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 16.
［実施例９１］
有機配位子１８（３７ｍｇ、０．０４ｍｍｏｌ）を用い、１２０℃で９０時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ９１を淡黄色の固体（２６ｍｇ）として得た。
[Example 91]
The same procedure as in Example 51 was performed except that organic ligand 18 (37 mg, 0.04 mmol) was used and heat treatment was performed at 120° C. for 90 hours to obtain MOF91 as a pale yellow solid (26 mg).
［実施例９２］
有機配位子１９（４２ｍｇ、０．０５ｍｍｏｌ）を用い、１２０℃で９０時間加熱処理する以外、実施例５１と同様に行い、ＭＯＦ９２を淡黄色の固体（４０ｍｇ）として得た。
[Example 92]
The same procedure as in Example 51 was performed except that organic ligand 19 (42 mg, 0.05 mmol) was used and heat treatment was performed at 120° C. for 90 hours to obtain MOF92 as a pale yellow solid (40 mg).
［実施例９３］
有機配位子１９（８４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で９０時間加熱処理する以外、実施例５３と同様に行い、ＭＯＦ９３を茶色の固体（５０ｍｇ）として得た。
[Example 93]
The same procedure as in Example 53 was performed except that organic ligand 19 (84 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 90 hours to obtain MOF93 as a brown solid (50 mg).
［実施例９４］
有機配位子１９（８４ｍｇ、０．１ｍｍｏｌ）を用い、１２０℃で４４時間加熱処理する以外、実施例５４と同様に行い、ＭＯＦ９４を白色の固体（１３０ｍｇ）として得た。
[Example 94]
The same procedure as in Example 54 was performed except that organic ligand 19 (84 mg, 0.1 mmol) was used and heat treatment was performed at 120° C. for 44 hours to obtain MOF94 as a white solid (130 mg).
実施例９１～９４で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１７に示す。 Regarding the metal-organic structures obtained in Examples 91 to 94, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 17.
［実施例９５］
有機配位子２０（７１ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２０中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６７時間加熱した以外は、実施例１と同様に行い、ＭＯＦ９５を淡黄色の固体（７６ｍｇ）として得た。
[Example 95]
Organic ligand 20 (71 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 20) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 67 hours in a sealed vial to obtain MOF95 as a pale yellow solid (76 mg).
実施例９５で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１８に示す。 Regarding the metal-organic framework obtained in Example 95, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 18.
［実施例９６］
有機配位子２１（６７ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２１中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で５日間加熱した以外は、実施例１と同様に行い、ＭＯＦ９６を淡黄色の固体（７６ｍｇ）として得た。
[Example 96]
Organic ligand 21 (67 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 21) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 5 days in a sealed vial to obtain MOF96 as a pale yellow solid (76 mg).
［実施例９７］
有機配位子２１（６７ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｒＣｌ４（９３ｍｇ、０．４ｍｍｏｌ、有機配位子２１中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び酢酸０．５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で５日間加熱した以外は、実施例１と同様に行い、ＭＯＦ９７を白色の固体（７６ｍｇ）として得た。
[Example 97]
Organic ligand 21 (67 mg, 0.1 mmol) and ZrCl 4 as a metal salt (93 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 21) were dissolved in 10 mL of DMF and 0.5 ml of acetic acid, The same procedure as in Example 1 was performed except that after filtration with a membrane filter, the mixture was heated at 120° C. for 5 days in a sealed vial to obtain MOF97 as a white solid (76 mg).
実施例９６及び９７で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表１９に示す。 Regarding the metal-organic structures obtained in Examples 96 and 97, the BET specific surface area and the hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 19.
［実施例９８］
有機配位子２２（７０ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２２中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ９８を淡黄色の固体（５９ｍｇ）として得た。
[Example 98]
Organic ligand 22 (70 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 22) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 68 hours in a sealed vial to obtain MOF98 as a pale yellow solid (59 mg).
［実施例９９］
有機配位子２２（７０ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｒＣｌ４（９３ｍｇ、０．４ｍｍｏｌ、有機配位子２２中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び酢酸０．５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ９９を白色の固体（７９ｍｇ）として得た。
[Example 99]
Organic ligand 22 (70 mg, 0.1 mmol) and ZrCl 4 as a metal salt (93 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 22) were dissolved in 10 mL of DMF and 0.5 ml of acetic acid, The same procedure as in Example 1 was performed except that after filtration with a membrane filter, the mixture was heated at 120° C. for 68 hours in a sealed vial to obtain MOF99 as a white solid (79 mg).
実施例９８及び９９で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２０に示す。 Regarding the metal-organic structures obtained in Examples 98 and 99, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 20.
［実施例１００］
有機配位子２３（７４ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２３中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１００を白色の固体（９３ｍｇ）として得た。
[Example 100]
Organic ligand 23 (74 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 23) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF100 as a white solid (93 mg).
［実施例１０１］
有機配位子２３（４６ｍｇ、０．０６ｍｍｏｌ）と金属塩としてＡｌＣｌ３・６Ｈ２Ｏ（５８ｍｇ、０．２４ｍｍｏｌ、有機配位子２３中のカルボン酸残基と当量）をＤＭＦ６ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４４時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０１を白色の固体（２４ｍｇ）として得た。
[Example 101]
Organic ligand 23 (46 mg, 0.06 mmol) and AlCl 3.6H 2 O (58 mg, 0.24 mmol, equivalent to the carboxylic acid residue in organic ligand 23) as a metal salt were dissolved in 6 mL of DMF, and the membrane was separated. The same procedure as in Example 1 was performed except that after filtration, the mixture was heated at 120° C. for 44 hours in a sealed vial to obtain MOF101 as a white solid (24 mg).
実施例１００及び１０１で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２１に示す。 Regarding the metal-organic structures obtained in Examples 100 and 101, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 21.
［実施例１０２］
有機配位子２４（３４ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（７５ｍｇ、０．２ｍｍｏｌ、有機配位子２４中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６７時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０２を淡黄色の固体（４５ｍｇ）として得た。
[Example 102]
Organic ligand 24 (34 mg, 0.05 mmol) and Al(NO 3 ) 3.9H 2 O (75 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 24) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 67 hours in a sealed vial to obtain MOF102 as a pale yellow solid (45 mg).
実施例１０２で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２２に示す。 Regarding the metal-organic framework obtained in Example 102, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 22.
［実施例１０３］
有機配位子２５（３２ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（７５ｍｇ、０．２ｍｍｏｌ、有機配位子２５中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０３を白色の固体（３２ｍｇ）として得た。
[Example 103]
Organic ligand 25 (32 mg, 0.05 mmol) and Al(NO 3 ) 3.9H 2 O (75 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 25) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 42 hours in a sealed vial to obtain MOF103 as a white solid (32 mg).
［実施例１０４］
有機配位子２５（３２ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＣｕ（ＮＯ２）２・３Ｈ２Ｏ（４９ｍｇ、０．２ｍｍｏｌ、有機配位子２５中のカルボン酸残基と当量）をＤＭＡ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０４を青色の固体（１８ｍｇ）として得た。
[Example 104]
Organic ligand 25 (32 mg, 0.05 mmol) and Cu(NO 2 ) 2.3H 2 O (49 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 25) as a metal salt were added to 5 mL of DMA. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 42 hours in a sealed vial to obtain MOF104 as a blue solid (18 mg).
［実施例１０５］
有機配位子２５（３２ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（５９ｍｇ、０．２ｍｍｏｌ、有機配位子２５中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０５を白色の固体（２３ｍｇ）として得た。
[Example 105]
Organic ligand 25 (32 mg, 0.05 mmol) and Zn(NO 3 ) 2.6H 2 O (59 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 25) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 42 hours in a sealed vial to obtain MOF105 as a white solid (23 mg).
実施例１０３～１０５で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２３に示す。 Regarding the metal-organic structures obtained in Examples 103 to 105, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 23.
［実施例１０６］
有機配位子２６（３９ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（７５ｍｇ、０．２ｍｍｏｌ、有機配位子２６中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０６を白色の固体（２４ｍｇ）として得た。
[Example 106]
Organic ligand 26 (39 mg, 0.05 mmol) and Al(NO 3 ) 3.9H 2 O (75 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 26) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 118 hours in a sealed vial to obtain MOF106 as a white solid (24 mg).
［実施例１０７］
有機配位子２６（３２ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（６０ｍｇ、０．２ｍｍｏｌ、有機配位子２６中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０７を白色の固体（４４ｍｇ）として得た。
[Example 107]
Organic ligand 26 (32 mg, 0.05 mmol) and Zn(NO 3 ) 2.6H 2 O (60 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 26) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 118 hours in a sealed vial to obtain MOF107 as a white solid (44 mg).
［実施例１０８］
有機配位子２６（３９ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＺｒＣｌ４（４７ｍｇ、０．２ｍｍｏｌ、有機配位子２６中のカルボン酸残基と当量）をＤＭＦ５ｍＬ及び酢酸０．２５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１８時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０８を白色の固体（５２ｍｇ）として得た。
[Example 108]
Organic ligand 26 (39 mg, 0.05 mmol) and ZrCl 4 as a metal salt (47 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 26) were dissolved in 5 mL of DMF and 0.25 ml of acetic acid, The same procedure as in Example 1 was performed except that after filtration with a membrane filter, the mixture was heated at 120° C. for 118 hours in a sealed vial to obtain MOF108 as a white solid (52 mg).
実施例１０６～１０８で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２４に示す。 Regarding the metal-organic structures obtained in Examples 106 to 108, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 24.
［実施例１０９］
有機配位子２７（７４ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２７中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１０９を白色の固体（８０ｍｇ）として得た。
[Example 109]
Organic ligand 27 (74 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 27) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF109 as a white solid (80 mg).
実施例１０９で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２５に示す。 Regarding the metal-organic framework obtained in Example 109, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 25.
［実施例１１０］
有機配位子２８（７０ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子２８中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１０を茶色の固体（８０ｍｇ）として得た。
[Example 110]
Organic ligand 28 (70 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 28) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF110 as a brown solid (80 mg).
［実施例１１１］
有機配位子２８（７０ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｎ（ＮＯ３）２・６Ｈ２Ｏ（１１８ｍｇ、０．４ｍｍｏｌ、有機配位子２８中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１１を淡黄色の固体（７０ｍｇ）として得た。
[Example 111]
Organic ligand 28 (70 mg, 0.1 mmol) and Zn(NO 3 ) 2.6H 2 O (118 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 28) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF111 as a pale yellow solid (70 mg).
［実施例１１２］
有機配位子２８（７０ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｒＣｌ４（９４ｍｇ、０．４ｍｍｏｌ、有機配位子２８中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び酢酸０．５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１６３時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１２を白色の固体（１０６ｍｇ）として得た。
[Example 112]
Organic ligand 28 (70 mg, 0.1 mmol) and ZrCl 4 as a metal salt (94 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 28) were dissolved in 10 mL of DMF and 0.5 ml of acetic acid, The same procedure as in Example 1 was performed except that after filtration with a membrane filter, the mixture was heated at 120° C. for 163 hours in a sealed vial to obtain MOF112 as a white solid (106 mg).
実施例１１０～１１２で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２６に示す。 Regarding the metal-organic structures obtained in Examples 110 to 112, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 26.
［実施例１１３］
有機配位子２９（６４ｍｇ、０．０９ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１３５ｍｇ、０．３６ｍｍｏｌ、有機配位子２９中のカルボン酸残基と当量）をＤＭＦ９ｍＬ及びギ酸１ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１５時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１３を白色の固体（６１ｍｇ）として得た。
[Example 113]
Organic ligand 29 (64 mg, 0.09 mmol) and Al(NO 3 ) 3.9H 2 O (135 mg, 0.36 mmol, equivalent to the carboxylic acid residue in organic ligand 29) as a metal salt were mixed in 9 mL of DMF and MOF113 was obtained as a white solid (61 mg) in the same manner as in Example 1, except that it was dissolved in 1 mL of formic acid, filtered through a membrane filter, and then heated at 120° C. for 115 hours in a sealed vial.
実施例１１３で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２７に示す。 Regarding the metal-organic framework obtained in Example 113, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 27.
［実施例１１４］
有機配位子３０（３３ｍｇ、０．０５ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（７５ｍｇ、０．２ｍｍｏｌ、有機配位子３０中のカルボン酸残基と当量）をＤＭＦ５ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で６７時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１４を白色の固体（５０ｍｇ）として得た。
[Example 114]
Organic ligand 30 (33 mg, 0.05 mmol) and Al(NO 3 ) 3.9H 2 O (75 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 30) as a metal salt were added to 5 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 67 hours in a sealed vial to obtain MOF114 as a white solid (50 mg).
［実施例１１５］
有機配位子３０（５２ｍｇ、０．０８ｍｍｏｌ）と金属塩としてＡｌＣｌ３・６Ｈ２Ｏ（７７ｍｇ、０．３２ｍｍｏｌ、有機配位子３０中のカルボン酸残基と当量）をＤＭＦ８ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で４４時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１５を白色の固体（２８ｍｇ）として得た。
[Example 115]
Organic ligand 30 (52 mg, 0.08 mmol) and AlCl 3.6H 2 O (77 mg, 0.32 mmol, equivalent to the carboxylic acid residue in organic ligand 30) as a metal salt were dissolved in 8 mL of DMF, and the membrane was separated. The same procedure as in Example 1 was performed except that after filtration, the mixture was heated at 120° C. for 44 hours in a sealed vial to obtain MOF115 as a white solid (28 mg).
実施例１１４～１１５で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２８に示す。 Regarding the metal-organic structures obtained in Examples 114 and 115, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 28.
［実施例１１６］
有機配位子３１（６８ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｒＣｌ４（９４ｍｇ、０．４ｍｍｏｌ、有機配位子３１中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及び酢酸０．５ｍｌに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で１１６時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１６を白色の固体（６２ｍｇ）として得た。
[Example 116]
Organic ligand 31 (68 mg, 0.1 mmol) and ZrCl 4 as a metal salt (94 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 31) were dissolved in 10 mL of DMF and 0.5 ml of acetic acid, The same procedure as in Example 1 was performed except that after filtration with a membrane filter, the mixture was heated at 120° C. for 116 hours in a sealed vial to obtain MOF116 as a white solid (62 mg).
［実施例１１７］
有機配位子３１（６８ｍｇ、０．１ｍｍｏｌ）と金属塩としてＺｒＣｌ４（９４ｍｇ、０．４ｍｍｏｌ、有機配位子３１中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及びギ酸１ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１７を白色の固体（８７ｍｇ）として得た。
[Example 117]
Organic ligand 31 (68 mg, 0.1 mmol) and ZrCl 4 as a metal salt (94 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 31) were dissolved in 10 mL of DMF and 1 mL of formic acid, and filtered through a membrane filter. After filtration, the same procedure as in Example 1 was performed except that the mixture was heated in a sealed vial at 120° C. for 91 hours to obtain MOF117 as a white solid (87 mg).
実施例１１６～１１７で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表２９に示す。 Regarding the metal-organic structures obtained in Examples 116 to 117, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 29.
［実施例１１８］
有機配位子３２（６７ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．４ｍｍｏｌ、有機配位子３２中のカルボン酸残基と当量）をＤＭＦ１０ｍＬ及びギ酸１ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１８を白色の固体（７９ｍｇ）として得た。
[Example 118]
Organic ligand 32 (67 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.4 mmol, equivalent to the carboxylic acid residue in organic ligand 32) as a metal salt were mixed in 10 mL of DMF and MOF118 was obtained as a white solid (79 mg) in the same manner as in Example 1, except that it was dissolved in 1 mL of formic acid, filtered through a membrane filter, and then heated at 120° C. for 92 hours in a sealed vial.
実施例１１８で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表３０に示す。 Regarding the metal-organic framework obtained in Example 118, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 30.
［実施例１１９］
有機配位子３３（６３ｍｇ、０．１ｍｍｏｌ）と金属塩としてＡｌ（ＮＯ３）３・９Ｈ２Ｏ（１５０ｍｇ、０．２ｍｍｏｌ、有機配位子３３中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９１時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１１９を白色の固体（７８ｍｇ）として得た。
[Example 119]
Organic ligand 33 (63 mg, 0.1 mmol) and Al(NO 3 ) 3.9H 2 O (150 mg, 0.2 mmol, equivalent to the carboxylic acid residue in organic ligand 33) as a metal salt were added to 10 mL of DMF. The same procedure as in Example 1 was performed except that the solution was dissolved, filtered through a membrane filter, and then heated at 120° C. for 91 hours in a sealed vial to obtain MOF119 as a white solid (78 mg).
［実施例１２０］
有機配位子３３（４０ｍｇ、０．０６ｍｍｏｌ）と金属塩としてＡｌＣｌ３・６Ｈ２Ｏ（５８ｍｇ、０．２４ｍｍｏｌ、有機配位子３３中のカルボン酸残基と当量）をＤＭＦ１０ｍＬに溶解し、メンブランフィルターでろ過後、密閉したバイアル中、１２０℃で９２時間加熱した以外は、実施例１と同様に行い、ＭＯＦ１２０を白色の固体（３９ｍｇ）として得た。
[Example 120]
Organic ligand 33 (40 mg, 0.06 mmol) and AlCl 3.6H 2 O (58 mg, 0.24 mmol, equivalent to the carboxylic acid residue in organic ligand 33) as a metal salt were dissolved in 10 mL of DMF, and the membrane was separated. The same procedure as in Example 1 was performed except that after filtration, the mixture was heated at 120° C. for 92 hours in a sealed vial to obtain MOF120 as a white solid (39 mg).
実施例１１９～１２０で得られた金属有機構造体について、実施例１と同様の方法でＢＥＴ比表面積及び７７Ｋ－大気圧における水素貯蔵量を測定した。その結果を表３１に示す。 Regarding the metal-organic structures obtained in Examples 119 to 120, the BET specific surface area and hydrogen storage amount at 77 K and atmospheric pressure were measured in the same manner as in Example 1. The results are shown in Table 31.
本発明の金属有機構造体は、水素等のガスを実用的な水準で貯蔵できる。そのため、燃料電池等の水素を利用したエネルギー分野に好適に使用できる。
The metal-organic framework of the present invention can store gases such as hydrogen at a practical level. Therefore, it can be suitably used in energy fields that utilize hydrogen, such as fuel cells.
Claims (6)
Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
ｎ１、ｎ２、ｎ３及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。
Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。
ｐは、１～３のいずれかの整数である。
Ｌは、単結合又は２～４価の有機基である。） A metal-organic structure formed by bonding a carboxylic acid ion represented by formula (1) with a polyvalent metal ion.
Each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
n1, n2, n3 and n4 are each independently an integer of 0 to 4.
When X is 2 or more, each X may be the same or different from each other.
p is an integer of 1 to 3.
L is a single bond or a divalent to tetravalent organic group. )
Ｒは、それぞれ独立に、水素原子、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
Ｘは、それぞれ独立に、ヒドロキシ基、Ｃ１～６アルキル基、Ｃ１～６アルコキシ基又はハロゲノ基である。
ｎ１、ｎ２、ｎ３及びｎ４は、それぞれ独立に、０～４のいずれかの整数である。
Ｘが２以上のとき、各Ｘは互いに同一でも異なっていてもよい。
Ｌａは、単結合又は２価の有機基である。） The metal-organic structure according to claim 1, wherein the carboxylic acid ion represented by formula (1) is a carboxylic acid ion represented by formula (2).
Each R is independently a hydrogen atom, a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
Each X is independently a hydroxy group, a C1-6 alkyl group, a C1-6 alkoxy group, or a halogeno group.
n1, n2, n3 and n4 are each independently an integer of 0 to 4.
When X is 2 or more, each X may be the same or different from each other.
L a is a single bond or a divalent organic group. )
A method for storing gas, comprising the step of bringing a gas into contact with the metal-organic structure according to any one of claims 1 to 4.
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