TWI809360B - 以具有聯三苯骨架之羧酸離子作為配位子之金屬有機結構體 - Google Patents
以具有聯三苯骨架之羧酸離子作為配位子之金屬有機結構體 Download PDFInfo
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- TWI809360B TWI809360B TW110107052A TW110107052A TWI809360B TW I809360 B TWI809360 B TW I809360B TW 110107052 A TW110107052 A TW 110107052A TW 110107052 A TW110107052 A TW 110107052A TW I809360 B TWI809360 B TW I809360B
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- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
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- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
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- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 2
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 2
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 2
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- DQBRPCBORUEKFU-UHFFFAOYSA-N CCCC(C=C(B(O)O)C=C1)=C1C(OCC)=O Chemical compound CCCC(C=C(B(O)O)C=C1)=C1C(OCC)=O DQBRPCBORUEKFU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 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
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- DGYIJVNZSDYBOE-UHFFFAOYSA-N [CH2]C1=CC=NC=C1 Chemical group [CH2]C1=CC=NC=C1 DGYIJVNZSDYBOE-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 150000001408 amides 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
- 125000005264 aryl amine group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 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
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000004639 dihydroindenyl group Chemical group C1(CCC2=CC=CC=C12)* 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
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005290 ethynyloxy group Chemical group C(#C)O* 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
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005280 halo alkyl sulfonyloxy group Chemical group 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 1
- 125000004995 haloalkylthio group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 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
- 229910000359 iron(II) sulfate 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
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-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
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 1
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 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
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 125000005146 naphthylsulfonyl group Chemical group C1(=CC=CC2=CC=CC=C12)S(=O)(=O)* 0.000 description 1
- 125000005029 naphthylthio group Chemical group C1(=CC=CC2=CC=CC=C12)S* 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OVPLZYJGTGDFNB-UHFFFAOYSA-N propan-2-yl carbamate Chemical compound CC(C)OC(N)=O OVPLZYJGTGDFNB-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 235000008160 pyridoxine Nutrition 0.000 description 1
- 239000011677 pyridoxine Substances 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RUPAXCPQAAOIPB-UHFFFAOYSA-N tert-butyl formate Chemical group CC(C)(C)OC=O RUPAXCPQAAOIPB-UHFFFAOYSA-N 0.000 description 1
- 125000000037 tert-butyldiphenylsilyl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1[Si]([H])([*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 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
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 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
- 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
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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Abstract
本發明之課題在於提供一種以具有聯三苯骨架之二羧酸作為有機配位子之新穎之金屬有機結構體及使用其之氣體儲藏方法。
本發明係一種式(I)所表示之羧酸離子與多價金屬離子鍵結而成之金屬有機結構體。(式(I)中,R1
及R2
分別獨立地表示羥基、未經取代或具有取代基之C1~6烷基等;R10
及R11
分別獨立地表示未經取代或具有取代基之C1~6烷基等;R20
表示未經取代或具有取代基之C1~6烷基等;其中,作為R1
、R2
、R3
、R4
、R5
、R6
、R7
、R8
、R10
、R11
、R20
上之取代基,羧基(COOH)及羧酸離子基(COO-
)除外;又,R10
及R11
不可同時為甲基)。
Description
本發明係關於一種以具有聯三苯骨架之羧酸離子作為配位子之新穎之金屬有機結構體及使用其等之氣體儲藏方法。本申請案對於2020年2月27日提出申請之日本專利申請第2020-032043號主張優先權,將其內容引用於本說明書中。
金屬有機結構體(以下有時稱為「MOF」)係藉由將金屬離子與連結該等之交聯性有機配位子進行組合而於內部具備具有空間(即細孔)之高分子結構的固體狀物質,作為具有氣體之儲藏或分離等功能之多孔性材料,十多年來引起了人們極大的興趣。已知將對苯二甲酸用作有機配位子之研究居多,將對苯二甲酸用作交聯性有機配位子,藉由於DMF(N,N-dimethylformamide,N,N-二甲基甲醯胺)中使用Zn(NO3
)2
・6H2
O之熱熔法所獲得之MOF-5於溫度77 K、4 MPa之條件下,可儲藏相對於MOF-5為7.1質量%之氫氣(參照專利文獻1及非專利文獻1~3)。
另一方面,已知藉由將氯化鋯及聯三苯二羧酸於二甲基甲醯胺中進行加熱所獲得之表面積為4000 m2
/g之MOF能夠儲藏氫氣、甲烷、乙炔等氣體(參照專利文獻2)。
又,已知藉由將下述式所表示之二羧酸及Fe2
CoO(CH3
COO)6
或Fe3
O(CH3
COO)6
於乙酸存在下,在N-甲基吡咯啶酮中以150℃加熱24小時,而以暗褐色結晶之形態獲得MOF,該MOF能夠儲藏氫氣、甲烷、二氧化碳、氮氣等氣體(參照專利文獻3)。
[化1]
先前技術文獻
專利文獻
專利文獻1:美國專利公開公報2010-75123號公報
專利文獻2:國際公開2009-133366號公報
專利文獻3:國際公開2015-079229號公報
非專利文獻
非專利文獻1:H. Li, M. Eddaudi, M. O'Keefe, O. M. Yaghi, Nature, 402, 276 (1999)
非專利文獻2:M. Eddaudi, J. Kim, N. Rosi, D. VodaK, J. Wachter, M. O'Keefe, O. M. Yaghi, Science 2002, 295 (5554), 469.
非專利文獻3:S. Kaye, A. Daily, O. M. Yaghi, J. Long, J. Am. Chem. Soc. 2007, 129 (46), 14176.
[發明所欲解決之問題]
已知MOF之結構會因所使用之金屬種類、配位子、反應條件而發生較大變化。關於以具有聯三苯骨架之二羧酸作為有機配位子之MOF,報告例較少。
本發明之課題在於提供一種以具有聯三苯骨架之二羧酸作為有機配位子之新穎之MOF及使用其之氣體儲藏方法。
[解決問題之技術手段]
本發明人等為了解決上述課題而進行了銳意研究,結果發現一種以於聯三苯骨架之特定位置具有特定取代基之化合物作為有機配位子而獲得之新穎之MOF。又,發現該等新穎之MOF具有較高之儲氫能力,從而完成本發明。
即,本發明係由以下所示之事項特定出之如下者。
[1]一種金屬有機結構體,其係式(I)所表示之羧酸離子與多價金屬離子鍵結而成者,
[化2]
(式(I)中,
R1
及R2
分別獨立地表示羥基、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(II)所表示之基;
[化3]
(式(II)中,R3
及R4
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基;*表示鍵結位置)
n表示R1
之數量且為0、1、2、3或4,n為2以上時,複數個R1
相互可相同,亦可不同;
m表示R2
之數量且為0、1、2、3或4,m為2以上時,複數個R2
相互可相同,亦可不同;
R10
及R11
分別獨立地表示未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(III)所表示之基;
[化4]
(式(III)中,R5
及R6
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基;*表示鍵結位置)
R20
表示未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(IV)所表示之基;
[化5]
(式(IV)中,R7
及R8
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基;*表示鍵結位置)
q表示R20
之數量且為0、1或2,q為2時,R20
相互可相同,亦可不同;
其中,作為R1
、R2
、R3
、R4
、R5
、R6
、R7
、R8
、R10
、R11
、R20
上之取代基,羧基(COOH)及羧酸離子基(COO-
)除外;又,R10
及R11
不可同時為甲基)。
[2]如[1]所記載之金屬有機結構體,其中式(I)所表示之羧酸離子為式(V)所表示之羧酸離子:
[化6]
(式中,R1
、R2
、R10
、R11
、n及m表示與式(I)相同之含義)。
[3]如[1]或[2]所記載之金屬有機結構體,其中多價金屬離子係選自由元素週期表之第2族~第13族之金屬所組成之群中之至少1種金屬之離子。
[4]如[1]至[3]中任一項所記載之金屬有機結構體,其中多價金屬離子係選自Zn、Fe、Co、Ni、Cu、Al、Zr、Ti、Cr及Mg之至少1種金屬之離子。
[5]如[1]至[4]中任一項所記載之金屬有機結構體,其進而包含除式(I)所表示之羧酸離子以外之有機配位子作為構成成分。
[6]一種氣體儲藏方法,其具有如下步驟:使氣體與如[1]至[5]中任一項所記載之金屬有機結構體接觸,將上述氣體吸附或吸藏於上述金屬有機結構體之內部。
[發明之效果]
本發明之MOF較為新穎,藉由使用本發明之MOF,能夠儲藏氫氣、二氧化碳、氮氣等氣體。
本發明之MOF係多價金屬離子與具有聯三苯骨架之二羧酸離子鍵結而成之MOF。
本發明中所使用之多價金屬離子若為2價以上之金屬離子,則並無特別限制,較佳為選自由元素週期表之第2族~第13族之金屬所組成之群中之至少1種金屬之離子,進而較佳為選自Zn、Fe、Co、Ni、Cu、Al、Zr、Ti、Cr及Mg之至少1種金屬之離子,進而較佳為選自Co、Ni、Cu、Zr、Ti、Cr及Zn之至少1種金屬之離子,該等可單獨使用1種,或可混合使用2種以上。
該等多價金屬離子以各種鹽之形式供給。作為金屬鹽,具體而言,可例舉:硝酸鋅(Zn(NO3
)2
・xH2
O)、硝酸鈦(Ti(NO3
)4
・xH2
O)、硝酸鈷(Co(NO3
)2
・xH2
O)、硝酸鐵(III)(Fe(NO3
)3
・xH2
O)、硝酸鐵(II)(Fe(NO3
)2
・xH2
O)、硝酸鎳(II)(Ni(NO3
)2
・xH2
O)、硝酸銅(II)(Cu(NO3
)2
・xH2
O);氯化鋅(ZnCl2
・xH2
O)、氯化鈦(TiCl4
・xH2
O)、氯化鋯(ZrCl4
・xH2
O)、氯化鈷(CoCl2
・xH2
O)、氯化鐵(III)(FeCl3
・xH2
O)、氯化鐵(II)(FeCl2
・xH2
O);乙酸鋅(Zn(CH3
COO)2
・xH2
O)、乙酸鈦(Ti(CH3
COO)4
・xH2
O)、乙酸鋯(Zr(CH3
COO)4
・xH2
O)、乙酸鈷(Co(CH3
COO)2
・xH2
O)、乙酸鐵(III)(Fe(CH3
COO)3
・xH2
O)、乙酸鐵(II)(Fe(CH3
COO)2
・xH2
O);硫酸鋅(ZnSO4
・xH2
O)、硫酸鈦(Ti(SO4
)2
・xH2
O)、硫酸鋯(Zr(SO4
)2
・xH2
O)、硫酸鈷(CoSO4
・xH2
O)、硫酸鐵(III)(Fe2
(SO4
)3
・xH2
O)、硫酸鐵(II)(FeSO4
・xH2
O);氫氧化鋅(Zn(OH)2
・xH2
O)、氫氧化鈦(Ti(OH)4
・xH2
O)、氫氧化鋯(Zr(OH)4
・xH2
O)、氫氧化鈷(Co(OH)2
・xH2
O)、氫氧化鐵(III)(Fe(OH)3
・xH2
O)、氫氧化鐵(II)(Fe(OH)2
・xH2
O);溴化鋅(ZnBr2
・xH2
O)、溴化鈦(TiBr4
・xH2
O)、溴化鋯(ZrBr4
・xH2
O)、溴化鈷(CoBr2
・xH2
O)、溴化鐵(III)(FeBr3
・xH2
O)、溴化鐵(II)(FeBr2
・xH2
O);碳酸鋅(ZnCO3
・xH2
O)、碳酸鈷(CoCO3
・xH2
O)、碳酸鐵(III)(Fe2
(CO3
)3
・xH2
O);氯氧化鋯(ZrOCl2
・xH2
O)等。再者,x為0~12之數。該等可單獨使用1種,或可混合使用2種以上。
本發明中所使用之具有聯三苯骨架之羧酸離子由下述式(I)表示。
[化7]
式(I)中,R1
及R2
分別獨立地表示羥基、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(II)所表示之基。
n表示R1
之數量且為0、1、2、3或4,n為2以上時,複數個R1
相互可相同,亦可不同。
m表示R2
之數量且為0、1、2、3或4,m為2以上時,複數個R2
相互可相同,亦可不同。
作為R1
及R2
之C1~6烷基,可為直鏈,亦可為支鏈,可例舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、2-甲基-正丁基、異己基等。
作為R1
及R2
之C3~8環烷基,可例舉:環丙基、環丁基、環戊基、環己基、立方烷基等。
R1
及R2
之C6~10芳基可為單環及多環之任一者,多環芳基只要至少一個環為芳香環,則其餘環可為飽和脂環、不飽和脂環或芳香環之任一者。具體而言,可例舉:苯基、萘基、薁基、茚基、二氫茚基、四氫萘基等。
作為R1
及R2
之3~6員雜環基,係包含選自由氮原子、氧原子及硫原子所組成之群中之1~4個雜原子作為環之構成原子者。雜環基可為單環及多環之任一者。多環雜環基只要至少一個環為雜環,則其餘環可為飽和脂環、不飽和脂環或芳香環之烴環之任一者。作為3~6員雜環基,可例舉:3~6員飽和雜環基、5~6員雜芳基、5~6員部分不飽和雜環基等。
作為3~6員飽和雜環基,可例舉:氮丙啶基、環氧基、吡咯啶基、四氫呋喃基、噻唑啶基、哌啶基、哌𠯤基、𠰌啉基、二氧戊環基、二氧雜環己基等。
作為5員雜芳基,可例舉:吡咯基、呋喃基、噻吩基、咪唑基、吡唑基、㗁唑基、異㗁唑基、噻唑基、異噻唑基、三唑基、㗁二唑基、噻二唑基、四唑基、吲哚基、異吲哚啉基、吲哚𠯤基、苯并咪唑基、咔唑基等。
作為6員雜芳基,可例舉:吡啶基、吡𠯤基、嘧啶基、嗒𠯤基、三𠯤基、喹啉基、異喹啉基、喹㗁啉基、㖕啉基、喹唑啉基、呔𠯤基、吖啶基、1-氮雜蒽基(naphthazinyl)、啡𠯤基等。
作為R1
及R2
之C1~6烷氧基,可例舉:甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、異丁氧基、第三丁氧基等。
作為R1
及R2
之C6~10芳氧基,可例舉:苯氧基、萘氧基、薁氧基、茚氧基、二氫茚氧基、四氫萘氧基等。
作為R1
及R2
之雜芳氧基,可例舉:呋喃氧基、噻唑氧基、吡啶氧基等。
作為R1
及R2
之鹵素基,可例舉:氟基、氯基、溴基、碘基等。
作為R1
及R2
之C1~6烷硫基,可例舉:甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、第二丁硫基、第三丁硫基等。
作為R1
及R2
之C6~10芳硫基,可例舉:苯硫基、萘硫基、薁硫基、茚硫基、二氫茚硫基、四氫萘硫基等。
作為R1
及R2
之雜芳硫基,可例舉:呋喃硫基、噻唑硫基、吡啶硫基等。
作為R1
及R2
之C1~6烷基亞磺醯基,可例舉:甲基亞磺醯基、乙基亞磺醯基、第三丁基亞磺醯基等。
作為R1
及R2
之C6~10芳基亞磺醯基,可例舉:苯基亞磺醯基、萘基亞磺醯基、薁基亞磺醯基、茚基亞磺醯基、二氫茚基亞磺醯基、四氫萘基亞磺醯基等。
作為R1
及R2
之雜芳基亞磺醯基,可例舉:呋喃基亞磺醯基、噻唑基亞磺醯基、吡啶基亞磺醯基等。
作為R1
及R2
之C1~6烷基磺醯基,可例舉:甲基磺醯基、乙基磺醯基、第三丁基磺醯基等。
作為R1
及R2
之C6~10芳基磺醯基,可例舉:苯基磺醯基、萘基磺醯基、薁基磺醯基、茚基磺醯基、二氫茚基磺醯基、四氫萘基磺醯基等。
作為R1
及R2
之雜芳基磺醯基,可例舉:呋喃基磺醯基、噻唑基磺醯基、吡啶基磺醯基等。
以下示出式(II)所表示之基。
[化8]
式(II)中,R3
及R4
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基。*表示鍵結位置。
作為R3
及R4
之C1~6烷基及C6~10芳基,可例舉與上述R1
及R2
中所例示者相同者。
作為R3
及R4
之C1~6烷羰基,可例舉:乙醯基、正丙醯基、異丙醯基、正丁醯基、異丁醯基、三甲基乙醯基、正戊醯基等。
作為R3
及R4
之C6~10芳基羰基,可例舉:苯甲醯基、1-萘基羰基、2-萘基羰基等。
作為式(II)所表示之基,可例舉:胺基、甲基胺基、二甲基胺基、乙基異丙基胺基、苯胺基、二苯基胺基、乙醯基胺基、苯甲醯基胺基等。
式(I)中,R10
及R11
分別獨立地表示未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(III)所表示之基。
作為R10
及R11
之C1~6烷基,可為直鏈,亦可為支鏈,可例舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、2-甲基-正丁基、異己基等。
作為R10
及R11
之C3~8環烷基、C6~10芳基、3~6員雜環基、C1~6烷氧基、C6~10芳氧基、雜芳氧基、鹵素基、C1~6烷硫基、C6~10芳硫基、雜芳硫基、C1~6烷基亞磺醯基、C6~10芳基亞磺醯基、雜芳基亞磺醯基、C1~6烷基磺醯基、C6~10芳基磺醯基及雜芳基磺醯基,可例舉與R1
及R2
中所例示者相同者。
以下示出式(III)所表示之基。
[化9]
式(III)中,R5
及R6
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基。*表示鍵結位置。式(III)中,作為R5
及R6
,可例舉與R3
及R4
中所例示者相同者,作為式(III)所表示之基,可例示與式(II)所表示之基中所例示者相同者。
式(I)中,R20
表示未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C3~8環烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之3~6員雜環基、未經取代或具有取代基之C1~6烷氧基、未經取代或具有取代基之C6~10芳氧基、未經取代或具有取代基之雜芳氧基、鹵素基、未經取代或具有取代基之C1~6烷硫基、未經取代或具有取代基之C6~10芳硫基、未經取代或具有取代基之雜芳硫基、未經取代或具有取代基之C1~6烷基亞磺醯基、未經取代或具有取代基之C6~10芳基亞磺醯基、未經取代或具有取代基之雜芳基亞磺醯基、未經取代或具有取代基之C1~6烷基磺醯基、未經取代或具有取代基之C6~10芳基磺醯基、未經取代或具有取代基之雜芳基磺醯基、氰基、硝基或式(IV)所表示之基。
q表示R20
之數量且為0、1或2,q為2時,R20
相互可相同,亦可不同。
作為R20
之C1~6烷基、C3~8環烷基、C6~10芳基、3~6員雜環基、C1~6烷氧基、C6~10芳氧基、雜芳氧基、鹵素基、C1~6烷硫基、C6~10芳硫基、雜芳硫基、C1~6烷基亞磺醯基、C6~10芳基亞磺醯基、雜芳基亞磺醯基、C1~6烷基磺醯基、C6~10芳基磺醯基及雜芳基磺醯基,可例舉與R1
及R2
中所例示者相同者。
以下示出式(IV)所表示之基。
[化10]
式(IV)中,R7
及R8
分別獨立地表示氫原子、未經取代或具有取代基之C1~6烷基、未經取代或具有取代基之C6~10芳基、未經取代或具有取代基之C1~6烷羰基或者未經取代或具有取代基之C6~10芳基羰基。*表示鍵結位置。式(IV)中,作為R7
及R8
,可例舉與R3
及R4
中所例示者相同者,作為式(IV)所表示之基,可例舉與式(II)所表示之基中所例示者相同者。
於本發明中,用語「未經取代之(unsubstituted)」意指只有作為母核之基。僅以作為母核之基之名稱記載時,若無特別說明,則意指「未經取代」。
另一方面,用語「具有取代基(substituted)」意指作為母核之基之任一氫原子被與母核相同或不同結構之基所取代。因此,「取代基」為與作為母核之基鍵結之其他基。取代基可為1個,亦可為2個以上。2個以上之取代基可相同,亦可不同,2個以上之取代基可與相同之原子鍵結,亦可與不同之原子鍵結。
「取代基」只要為化學上所容許,且具有本發明之效果即可,無特別限制。
作為可成為「取代基」之基之具體例,可例舉以下之基。
甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基等C1~6烷基;
乙烯基、1-丙烯基、2-丙烯基(烯丙基)、丙烯-2-基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基等C2~6烯基;
乙炔基、1-丙炔基、2-丙炔基(炔丙基)、1-丁炔基、2-丁炔基、3-丁炔基、1-甲基-2-丙炔基等C2~6炔基;
環丙基、環丁基、環戊基、環己基、立方烷基等C3~8環烷基;
苯基、萘基等C6~10芳基;
苄基、苯乙基等C6~10芳基C1~6烷基;
3~6員雜環基;
3~6員雜環基C1~6烷基;
側氧基;
羥基;
甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、異丁氧基、第三丁氧基等C1~6烷氧基;
乙烯氧基、烯丙氧基、1-丙烯氧基、丙烯-2-基氧基、3-丁烯氧基、2-丁烯氧基等C2~6烯氧基;
乙炔氧基、炔丙氧基等C2~6炔氧基;
苯氧基、萘氧基等C6~10芳氧基;
苄氧基、苯乙氧基等C6~10芳基C1~6烷氧基;
噻唑氧基、吡啶氧基等5~6員雜芳氧基;
噻唑基甲氧基、吡啶基甲氧基等5~6員雜芳基C1~6烷氧基;
甲醯基;
乙醯基、丙醯基等C1~6烷羰基;
甲醯氧基;
乙醯氧基、丙醯氧基等C1~6烷基羰氧基;
苯甲醯基等C6~10芳基羰基;
甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、第三丁氧基羰基等C1~6烷氧基羰基;
甲氧基羰氧基、乙氧基羰氧基、正丙氧基羰氧基、異丙氧基羰氧基、正丁氧基羰氧基、第三丁氧基羰氧基等C1~6烷氧基羰氧基;
氟基、氯基、溴基、碘基等鹵素基;
氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、五氟乙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、全氟丙基、2,2,2-三氟-1-三氟甲基乙基、全氟異丙基、4-氟丁基、2,2,3,3,4,4,4-七氟丁基、全氟丁基、全氟戊基、全氟己基、氯甲基、溴甲基、二氯甲基、二溴甲基、三氯甲基、三溴甲基、1-氯乙基、2,2,2-三氯乙基、4-氯丁基、全氯己基、2,4,6-三氯己基等C1~6鹵烷基;
2-氯-1-丙烯基、2-氟-1-丁烯基等C2~6鹵烯基;
4,4-二氯-1-丁炔基、4-氟-1-戊炔基、5-溴-2-戊炔基等C2~6鹵炔基;
三氟甲氧基、2-氯-正丙氧基、2,3-二氯丁氧基等C1~6鹵烷氧基;
2-氯丙烯氧基、3-溴丁烯氧基等C2~6鹵烯氧基;
氯乙醯基、三氟乙醯基、三氯乙醯基等C1~6鹵烷羰基;
胺基;
甲基胺基、二甲基胺基、二乙基胺基等經單C1~6烷基取代之胺基或經二C1~6烷基取代之胺基(於後者之情形時,C1~6烷基可相同,亦可不同);
苯胺基、萘胺基等C6~10芳基胺基;
苄基胺基、苯乙基胺基等C6~10芳基C1~6烷基胺基;
甲醯胺基;
乙醯基胺基、丙醯基胺基、丁醯基胺基、異丙基羰基胺基等C1~6烷基羰基胺基;
甲氧基羰基胺基、乙氧基羰基胺基、正丙氧基羰基胺基、異丙氧基羰基胺基等C1~6烷氧基羰基胺基;
S,S-二甲基磺醯基亞胺基等C1~6烷基磺醯基亞胺基;
胺基羰基、二甲基胺基羰基、苯基胺基羰基、N-苯基-N-甲基胺基羰基等未經取代或具有取代基之胺基羰基;
亞胺基甲基、1-亞胺基乙基、1-亞胺基-正丙基等亞胺基C1~6烷基;
N-羥基-亞胺基甲基、1-(N-羥基亞胺基)乙基、1-(N-羥基亞胺基)丙基、N-甲氧基亞胺基甲基、1-(N-甲氧基亞胺基)乙基等經取代或未經取代之N-羥基亞胺基C1~6烷基;
羥基亞胺基;
甲氧基亞胺基、乙氧基亞胺基、正丙氧基亞胺基、異丙氧基亞胺基、正丁氧基亞胺基等C1~6烷氧基亞胺基;
胺基羰氧基;
乙基胺基羰氧基、二甲基胺基羰氧基等經單C1~6烷基取代之胺基羰氧基或經二C1~6烷基取代之胺基羰氧基(於後者之情形時,C1~6烷基可相同,亦可不同);
側硫基;
硫醇(巰)基;
甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、第二丁硫基、第三丁硫基等C1~6烷硫基;
三氟甲硫基、2,2,2-三氟乙硫基等C1~6鹵烷硫基;
苯硫基、萘硫基等C6~10芳硫基;
噻唑硫基、吡啶硫基等5~6員雜芳硫基;
甲基亞磺醯基、乙基亞磺醯基、第三丁基亞磺醯基等C1~6烷基亞磺醯基;
三氟甲基亞磺醯基、2,2,2-三氟乙基亞磺醯基等C1~6鹵烷基亞磺醯基;
苯基亞磺醯基等C6~10芳基亞磺醯基;
噻唑基亞磺醯基、吡啶基亞磺醯基等5~6員雜芳基亞磺醯基;
甲基磺醯基、乙基磺醯基、第三丁基磺醯基等C1~6烷基磺醯基;
三氟甲基磺醯基、2,2,2-三氟乙基磺醯基等C1~6鹵烷基磺醯基;
苯基磺醯基等C6~10芳基磺醯基;
噻唑基磺醯基、吡啶基磺醯基等5~6員雜芳基磺醯基;
磺基;
甲基磺醯氧基、乙基磺醯氧基、第三丁基磺醯氧基等C1~6烷基磺醯氧基;
三氟甲基磺醯氧基、2,2,2-三氟乙基磺醯氧基等C1~6鹵烷基磺醯氧基;
三甲基矽烷基、三乙基矽烷基、第三丁基二甲基矽烷基等經三C1~6烷基取代之矽烷基;
三苯基矽烷基等經三C6~10芳基取代之矽烷基;
烯丙基二甲基矽烷基、乙烯基二甲基矽烷基等經C2~C6烯基C1~C6二烷基取代之矽烷基;
第三丁基二苯基矽烷基、二苯基甲基矽烷基等經C1~C6烷基二C6~C10芳基取代之矽烷基;
二甲基苯基矽烷基等經二C1~C6烷基C6~C10芳基取代之矽烷基;
苄基二甲基矽烷基、3-苯基丙基二甲基矽烷基等(C6~C10苯基C1~C6烷基)二C1~C6烷基矽烷基;
甲基苯基乙烯基矽烷基等C1~C6烷基C6~C10芳基C2~C6烯基矽烷基;
三甲氧基矽烷基、三乙氧基矽烷基等經三C1~C6烷氧基取代之矽烷基;
二甲基矽烷基、二乙基矽烷基等經二C1~C6烷基取代之矽烷基;
二甲氧基矽烷基、二乙氧基矽烷基等經二C1~C6烷氧基取代之矽烷基;
甲氧基二甲基矽烷基等經C1~C6烷氧基二C1~C6烷基取代之矽烷基;
第三丁氧基二苯基矽烷基等經C1~C6烷氧基二C6~C10芳基取代之矽烷基;
甲基二甲氧基矽烷基等經C1~C6烷基二C1~C6烷氧基取代之矽烷基;
氰基;
硝基。
又,上述所謂「3~6員雜環基」,係包含選自由氮原子、氧原子及硫原子所組成之群中之1~4個雜原子作為環之構成原子者。雜環基可為單環及多環之任一者。多環雜環基只要至少一個環為雜環,則其餘環可為飽和脂環、不飽和脂環或芳香環之烴環之任一者。作為「3~6員雜環基」,可例舉3~6員飽和雜環基、5~6員雜芳基、5~6員部分不飽和雜環基等。
作為3~6員飽和雜環基,可例舉:氮丙啶基、環氧基、吡咯啶基、四氫呋喃基、噻唑啶基、哌啶基、哌𠯤基、𠰌啉基、二氧戊環基、二氧雜環己基等。
作為5員雜芳基,可例舉:吡咯基、呋喃基、噻吩基、咪唑基、吡唑基、㗁唑基、異㗁唑基、噻唑基、異噻唑基、三唑基、㗁二唑基、噻二唑基、四唑基、吲哚基、異吲哚啉基、吲哚𠯤基、苯并咪唑基、咔唑基等。
作為6員雜芳基,可例舉:吡啶基、吡𠯤基、嘧啶基、嗒𠯤基、三𠯤基、喹啉基、異喹啉基、喹㗁啉基、㖕啉基、喹唑啉基、呔𠯤基、吖啶基、1-氮雜蒽基(naphthazinyl)、啡𠯤基等。
作為5~6員部分不飽和雜環基,可例舉:異㗁啉基、吡唑啉基等。
作為3~6員雜環基1~6烷基,可例舉:縮水甘油基、2-四氫呋喃基甲基、2-吡咯基甲基、2-咪唑基甲基、3-異㗁唑基甲基、5-異㗁唑基甲基、2-吡啶基甲基、4-吡啶基甲基、3-異㗁啉基甲基等。
「C1~6」等用語表示作為母核之基之碳原子數為1~6個等。該碳原子數中,不包含位於取代基中之碳原子之數。例如,乙氧基丁基之作為母核之基為丁基,取代基為乙氧基,因此分類為C2烷氧基C4烷基。
其中,於使用「C1~6烷羰基」、「C6~10芳基羰基」之用語之情形時,碳原子數中不包含羰基之碳。
關於該等「取代基」,該取代基中之任一氫原子可被不同結構之基取代。
其中,式(I)中,作為R1
、R2
、R3
、R4
、R5
、R6
、R7
、R8
、R10
、R11
、R20
上之取代基,羧基(COOH)及羧酸離子基(COO-
)除外。該情況例如於R1
為烷基之情形時,表示羧基烷基不包含於取代烷基中。又,R10
及R11
不可同時為甲基。
作為式(I)所表示之羧酸離子,只要為滿足式(I)所表示之化學式之條件者,則無特別限定,羧酸離子基之取代位置、R1
、R2
及R20
之取代位置等可任意選擇,其中較佳為下述式(V)所表示之羧酸離子。
[化11]
式(V)中,R1
、R2
、R10
、R11
、n及m表示與式(I)相同之含義。
作為式(V)所表示之羧酸離子,具體而言,可例舉以下之式中所表示之化合物等。
[化12]
[化13]
[化14]
[化15]
[化16]
本發明之金屬有機結構體可包含除式(I)所表示之羧酸離子以外之有機配位子。作為此種有機配位子,可例舉:對苯二甲酸、鄰苯二甲酸、間苯二甲酸、5-氰基間苯二甲酸、1,3,5-均苯三酸、1,3,5-三(4-羧基苯基)苯、4,4'-二羧基聯苯、3,5-二羧基吡啶、2,3-二羧基吡𠯤、1,3,5-三(4-羧基苯基)苯、1,2,4,5-四(4-羧基苯基)苯、9,10-蒽二甲酸、2,6-萘二甲酸、[1,1':4',1"]聯三苯-3,3",5,5"-四羧酸、聯苯-3,3",5,5"-四羧酸、3,3',5,5'-四羧基二苯甲烷、1,3,5-三(4'-羧基[1,1'-聯苯]-4-基)苯、1,3,5-三(4-羧基苯基)三𠯤、1,2-雙(4-羧基-3-硝基苯基)乙烯、1,2-雙(4-羧基-3-胺基苯基)乙烯、反式,反式-己二烯二酸、反丁烯二酸、苯并咪唑、咪唑、1,4-二氮雜雙環[2.2.2]辛烷(DABCO)、吡𠯤、4,4'-聯吡啶、1,2-二(4-吡啶基)乙烯、2,7-二氮雜芘、4,4'-偶氮雙吡啶、雙(3-(4-吡啶基)-2,4-戊二酮酸)銅等。
於使用式(I)所表示之羧酸離子及除式(I)所表示之羧酸離子以外之有機配位子之情形時,混合莫耳比並無特別限制,例如,只要為使用除式(I)所表示之羧酸離子以外之有機配位子作為支柱分子,藉由該支柱分子交聯,構建如支柱層型之三維結構之情形,則相對於式(I)所表示之羧酸離子,較佳為過量使用除式(I)所表示之羧酸離子以外之有機配位子。
作為本發明之金屬有機結構體之製造方法,並無特別限制,亦可使用如下等任一方法:溶劑擴散法、溶劑攪拌法、水熱法等溶液法;微波法,其對反應溶液照射微波而將系統整體於短時間內均勻地進行加熱;超音波法,其藉由對反應容器照射超音波,於反應容器中反覆發生壓力之變化,由於該壓力之變化,產生溶劑形成氣泡並崩壞之稱作空蝕之現象,此時約5000 K、10000 bar之高能量場成為局部形成之結晶之各生成之反應場;固相合成法,其不使用溶劑,而將金屬離子產生源與有機配位子進行混合;LAG(liquid assisted grinding,液體輔助研磨法)法,其添加結晶水程度之水將金屬離子產生源與有機配位子進行混合。
例如,包括如下步驟:分別製備含有作為金屬離子之產生源之金屬化合物及溶劑的第一溶液、含有式(I)所表示之羧酸離子或作為其前驅物之羧酸及溶劑的第二溶液、及視需要之含有其他作為多牙配位子之化合物及溶劑的第三溶液;及將第一溶液與第二溶液及第三溶液進行混合而製備反應液,藉由加熱該反應液,獲得金屬有機結構體。第一~第三溶液無需分開製備,例如,亦可將上述金屬化合物、式(I)所表示之羧酸離子或作為其前驅物之羧酸、其他作為多牙配位子之化合物及溶劑同時混合而製備1個溶液。
上述金屬化合物與式(I)所表示之羧酸離子或作為其前驅物之羧酸之混合莫耳比可根據所要獲得之金屬有機結構體之細孔尺寸、表面特性而任意地選擇,相對於式(I)所表示之羧酸離子或作為其前驅物之羧酸1莫耳,較佳為使用1莫耳以上之金屬化合物,進而較佳為使用1.1莫耳以上,進而較佳為使用1.2莫耳以上,進而較佳為使用1.5莫耳以上,進而較佳為使用2莫耳以上,進而較佳為使用3莫耳以上。
反應液中之上述金屬離子之濃度較佳為25~200莫耳/L之範圍。
式(I)所表示之羧酸離子或作為其前驅物之羧酸於反應液中之濃度較佳為10~100莫耳/L之範圍。
除式(I)所表示之羧酸離子或作為其前驅物之羧酸以外之有機配位子於反應液中之濃度較佳為25~100莫耳/L。
作為所使用之溶劑,並無特別限定,可使用選自由N,N-二甲基甲醯胺(以下有時記載為「DMF」)、N,N-二乙基甲醯胺(以下有時記載為「DEF」)、N,N-二甲基乙醯胺(以下有時記載為「DMA」)及水所組成之群中之1種或2種以上。其中,較佳為單獨使用DMF、DEF或DMA之任一者,或者使用DMF/水混合溶劑、DEF/水混合溶劑或DMA/水混合溶劑。
反應液之加熱溫度並無特別限制,較佳為室溫~140℃之範圍。
本發明之金屬有機結構體藉由吸附或吸藏氫氣、甲烷、乙炔、二氧化碳、氮氣等氣體,可儲藏上述氣體。
使用本發明之金屬有機結構體之氣體儲藏方法並無特別限制,較佳為使氣體與本發明之金屬有機結構體接觸之方法,接觸之方法並無特別限制。例如,可例舉如下方法等:於罐中填充本發明之金屬有機結構體而形成氣體儲藏罐,使氣體流入該罐內;使構成罐之內壁之表面擔載本發明之金屬有機結構體而形成氣體儲藏罐,使氣體流入該罐內;及利用包含本發明之金屬有機結構體之材料使罐成形而形成氣體儲藏罐,使氣體流入該罐內。
[實施例]
以下,使用實施例對本發明詳細地進行說明,但本發明並不限定於實施例之範圍。
作為成為構成本發明之金屬有機結構體之式(I)所表示之羧酸離子之前驅物的羧酸,使用以下表1所示之有機配位子1~19。
[表1]
有機配位子1 | 有機配位子2 |
有機配位子3 | 有機配位子4 |
有機配位子5 | 有機配位子6 |
有機配位子7 | 有機配位子8 |
有機配位子9 | 有機配位子10 |
有機配位子11 | 有機配位子12 |
有機配位子13 | 有機配位子14 |
有機配位子15 | 有機配位16 |
有機配位子17 | 有機配位子18 |
有機配位子19 | |
[製造例1]有機配位子1之合成
將1,4-二溴-2,5-二乙基苯(2.5 mmol)、4-甲氧基羰基苯基硼酸(7.5 mmol)、四(三苯基膦)鈀(0)(0.25 mmol)、氟化銫(1.25 mmol)、碳酸銫(7.5 mmol)、1,4-二㗁烷25 mL、水1 mL之溶液於氮氣下,於100℃下加熱一夜。將反應液恢復至室溫,加水並進行分液,利用硫酸鎂將以二氯甲烷提取之有機層進行乾燥,過濾,減壓並蒸餾去除溶劑,使用矽膠管柱層析法(氯仿)將所獲得之固體純化,以無色固體之形態獲得2.1 mmol之2',5'-二乙基[1,1':4',1"-聯三苯]-4,4"-二羧酸二甲酯。將所獲得之2',5'-二乙基[1,1':4',1"-聯三苯]-4,4"-二羧酸二甲酯2.0 mmol、氫氧化鉀(20 mmol)、四氫呋喃20 mL、水10 mL之溶液加熱回流2天。將反應液恢復至室溫,蒸餾去除四氫呋喃之後添加濃鹽酸,將析出之固體進行過濾、水洗,將所獲得之固體於100℃下進行乾燥,藉此以無色固體之形態獲得2.0 mmol之2',5'-二乙基[1,1':4',1"-聯三苯]-4,4"-二羧酸。
[製造例2]~[製造例13]
使用以下表2所示之試劑代替1,4-二溴-2,5-二乙基苯,除此以外,以與製造例1相同之操作進行,均以無色固體之形態獲得有機配位子2~13。
[表2]
製造例 | 試劑 |
1 | 1,4-二溴-2,5-二乙基苯 |
2 | 1,4-二溴-2,5-二正丙基苯 |
3 | 1,4-二溴-2,5-二異丙基苯 |
4 | 1,4-二溴-2,5-二正丁基苯 |
5 | 1,4-二溴-2,5-二環己基苯 |
6 | 1,4-二溴-2,5-二甲氧基苯 |
7 | 1,4-二溴-2,5-二乙氧基苯 |
8 | 1,4-二溴-2,5-二正丙氧基苯 |
9 | 1,4-二溴-2,5-二異丙氧基苯 |
10 | 1,4-二溴-2,5-二正丁氧基苯 |
11 | 1,4-二溴-2-異丙基-5-甲基苯 |
12 | 1,4-二溴-2-甲氧基-5-甲基苯 |
13 | 1,4-二溴-2-氯-5-甲基苯 |
[製造例14]
使用1,4-二溴-2,5-二甲氧基苯代替製造例1之1,4-二溴-2,5-二乙基苯,使用3-羥基-4-乙氧基羰基苯基硼酸代替4-甲氧基羰基苯基硼酸,除此以外,以與製造例1相同之操作進行,以無色固體之形態獲得有機配位子14。
[製造例15]
將製造例14中合成之3,3"-二羥基-2',5'-二甲氧基-[1,1':4',1"-聯三苯]-4,4"-二羧酸二乙酯(1.0 mmol)、碳酸鉀(3.0 mmol)、碘甲烷(4.0 mmol)溶解於DMF 10 mL中,於100℃下攪拌一夜。將反應液恢復至室溫並添加水,利用硫酸鎂將以乙酸乙酯提取之有機層進行乾燥並過濾,於減壓下蒸餾濾液。利用矽膠管柱層析法(氯仿)將所獲得之固體分離純化,藉此以無色固體之形態獲得2',3,3",5'-四甲氧基-[1,1':4',1"-聯三苯]-4,4"-二羧酸二乙酯。於所獲得之無色固體中添加氫氧化鉀(10.0 mmol)、乙醇20 mL、水10 mL並於90℃下攪拌一夜。恢復至室溫,添加稀鹽酸並將所析出之固體進行過濾,利用水充分清洗並進行乾燥,藉此以無色固體之形態獲得有機配位子15之2',3,3",5'-四甲氧基-[1,1':4',1"-聯三苯]-4,4"-二羧酸。
[製造例16]
使用碘丙烷代替製造例15中所使用之碘甲烷,除此以外,藉由與製造例15相同之操作以無色固體之形態獲得有機配位子16。
[製造例17]~[製造例19]
使用以下表3所示之試劑,除此以外,以與製造例14相同之操作進行,均以無色固體之形態獲得有機配位子17~19。
[表3]
製造例 | 試劑 |
17 | 3-甲基-4-乙氧基羰基苯基硼酸 |
18 | 3-氯-4-乙氧基羰基苯基硼酸 |
19 | 3-正丙基-4-乙氧基羰基苯基硼酸 |
[實施例1-1]
於有機配位子1(0.3 mmol)、硝酸鋅六水合物(0.6 mmol)中添加DMF 6 mL,將所獲得之溶液藉由烘箱(反應條件:120℃、24小時)進行加熱。使反應液恢復至室溫,去除上清液。使用DMF 10 mL洗淨殘渣後,去除溶劑,於殘渣中添加氯仿10 mL,浸漬一夜。將自殘渣浸漬液去除氯仿所獲得之固體於150℃下進行真空乾燥5小時,以無色固體之形態獲得金屬有機結構體1-1。
[實施例1-2]~[實施例1-16]
使用下述表4所示之有機配位子及溶劑,於表4所示之反應條件下進行反應,除此以外,進行與實施例1-1相同之操作,獲得金屬有機結構體1-2~1-16。將其結果示於表4。
[表4]
實施例 | 有機配位子 | 溶劑 | 溫度(℃) | 加熱時間(hr) | 性狀 |
1-1 | 1 | DMF | 120 | 24 | 無色固體 |
1-2 | 1 | DEF | 120 | 24 | 淡黃色固體 |
1-3 | 1 | DMF | 90 | 12 | 無色固體 |
1-4 | 2 | DMF | 90 | 24 | 無色固體 |
1-5 | 2 | DMF | 120 | 24 | 無色固體 |
1-6 | 2 | DEF | 90 | 24 | 無色固體 |
1-7 | 2 | DEF | 120 | 24 | 無色固體 |
1-8 | 3 | DMF | 90 | 24 | 無色固體 |
1-9 | 3 | DMF | 120 | 24 | 無色固體 |
1-10 | 3 | DEF | 90 | 24 | 無色固體 |
1-11 | 3 | DEF | 120 | 24 | 無色固體 |
1-12 | 14 | DMF | 120 | 24 | 黃褐色固體 |
1-13 | 15 | DMF | 120 | 24 | 灰白色粉末 |
1-14 | 16 | DMF | 120 | 24 | 灰白色粉末 |
1-15 | 17 | DMF | 120 | 24 | 灰白色粉末 |
1-16 | 19 | DMF | 120 | 24 | 灰白色粉末 |
[實施例2-1]
於有機配位子1(0.375 mmol)、硝酸鋅六水合物(0.375 mmol)、作為輔助配位子之1,4-二氮雜雙環[2.2.2]辛烷(0.20 mmol)中添加作為溶劑之DMF 7.5 mL,將所得之溶液攪拌15分鐘後,照射超音波。藉由烘箱(反應條件:120℃、48小時)對將該混合液進行過濾所獲得之溶液進行加熱。將反應液恢復至室溫,將析出之固體以DMF 10 mL洗淨3次後,使用氯仿10 mL進一步洗淨3次。將所獲得之固體於氯仿10 mL中浸漬一夜,將加壓過濾所獲得之固體於150℃下真空乾燥5小時,藉此以無色結晶之形態獲得金屬有機結構體2-1。
[實施例2-2]
使用有機配位子2代替有機配位子1,除此以外,進行與實施例2-1相同之操作,以乳綠色固體之形態獲得金屬有機結構體2-2。
[實施例3-1]
將有機配位子1(0.5 mmol)溶解於DMF 7 mL中,於其中添加三乙胺(2.0 mmol),進而滴加乙酸鋅二水合物(1.27 mmol)之DMF 8 mL溶液,將所獲得之溶液於室溫下攪拌20小時,靜置。將反應液離心分離之後去除上清液,將所獲得之固體於DMF 20 mL中浸漬一晩。其後去除固體浸漬液之上清液,將所獲得之固體於氯仿20 mL中浸漬一晩後將固體分離,將該操作重複3次。其後,藉由將分離之固體於150℃下真空乾燥5小時,以淺灰色粉末之形態獲得金屬有機結構體3-1。
[實施例3-2]~[實施例3-11]
使用下述表5所示之有機配位子,於表5所示之反應條件下進行反應,除此以外,進行與實施例3-1相同之操作,獲得金屬有機結構體3-2~3-11。將其結果示於表5。
[表5]
實施例 | 有機配位子 | 鹼 | 攪拌時間(hr) | 性狀 |
3-1 | 1 | Et3 N | 20 | 淺灰色粉末 |
3-2 | 1 | 無 | 2.5 | 無色粉末 |
3-3 | 2 | 無 | 2.5 | 無色粉末 |
3-4 | 2 | Et3 N | 2.5 | 無色粉末 |
3-5 | 3 | 無 | 2.5 | 無色粉末 |
3-6 | 5 | 無 | 2.5 | 無色粉末 |
3-7 | 6 | 無 | 2.5 | 無色粉末 |
3-8 | 7 | 無 | 2.5 | 無色粉末 |
3-9 | 8 | 無 | 2.5 | 無色粉末 |
3-10 | 9 | 無 | 2.5 | 無色粉末 |
3-11 | 10 | 無 | 2.5 | 無色粉末 |
[實施例4-1]
於有機配位子1(0.3 mmol)、硝酸鋅六水合物(0.4 mmol)之DMF 10 mL溶液中,於攪拌下滴加三乙胺0.5 mL,於室溫下攪拌5分鐘。將反應混合物離心分離後,去除上清液,於殘渣中添加DMF 10 mL,再次進行離心分離10分鐘,去除上清液。將殘渣於DMF中浸漬一夜後,進行離心分離10分鐘,去除上清液後,於殘渣中添加氯仿10 mL。將對殘渣浸漬液進一步進行離心分離所獲得之固體於氯仿20 mL中浸漬一晩並進行離心分離,將該操作重複3次。其後,藉由將進行離心分離所獲得之固體於150℃下真空乾燥5小時,以淺灰色粉末之形態獲得金屬有機結構體4-1。
[實施例4-2]
使用有機配位子2代替有機配位子1,除此以外,藉由與實施例4-1相同之操作,以無色粉末之形態獲得金屬有機結構體4-2。
[實施例4-3]~[實施例4-8]
使用下述表6所示之有機配位子,於表6所示之反應條件下進行反應,除此以外,進行與實施例4-1相同之操作,獲得金屬有機結構體4-3~4-8。將其結果示於表6。
[表6]
實施例 | 有機配位子 | 性狀 |
4-3 | 5 | 無色粉末 |
4-4 | 6 | 無色粉末 |
4-5 | 7 | 無色粉末 |
4-6 | 8 | 無色粉末 |
4-7 | 9 | 無色粉末 |
4-8 | 10 | 無色粉末 |
[實施例5-1]
於有機配位子1(0.2 mmol)、硝酸銅三水合物(0.2 mmol)中添加DMF 4 mL,對所獲得之溶液照射超音波15分鐘。將對該溶液進行過濾所獲得之溶液於120℃下進行加熱25小時。將反應液恢復至室溫後,進行離心分離10分鐘,去除上清液,於殘渣中加入DMF 10 mL,再次進行離心分離10分鐘,去除上清液。將殘渣於DMF中浸漬一夜後,進行離心分離10分鐘,藉由加壓過濾去除DMF後,於所獲得之固體中添加氯仿10 mL。將對固體浸漬液進一步進行離心分離所獲得之固體於氯仿20 mL中浸漬一晩並進行離心分離,將該操作重複3次。其後,藉由將加壓過濾所獲得之固體於150℃下真空乾燥5小時,獲得金屬有機結構體5-1。
[實施例5-2]~[實施例5-7]
使用下述表7所示之有機配位子,於表7所示之反應條件下進行反應,除此以外,進行與實施例5-1相同之操作,獲得金屬有機結構體5-2~5-7。將其結果示於表7。
[表7]
實施例 | 有機配位子 | 溶劑 | 溫度(℃) | 加熱時間(hr) | 性狀 |
5-1 | 1 | DMF | 120 | 25 | 綠色固體 |
5-2 | 1 | DMF | 90 | 25 | 淡藍色固體 |
5-3 | 1 | DEF | 120 | 25 | 淡藍色固體 |
5-4 | 1 | DEF | 90 | 25 | 淡藍色固體 |
5-5 | 2 | DMF | 120 | 40 | 紫色固體 |
5-6 | 2 | DMF | 90 | 40 | 紫色固體 |
5-7 | 4 | DMF | 120 | 24 | 紫色固體 |
[實施例6-1]
將有機配位子1(0.4 mmol)、硝酸鎳六水合物(0.8 mmol)之THF 9 mL、水1 mL之溶液於100℃下進行加熱48小時。將反應液恢復至室溫後,去除上清液,於殘渣中加入DMF,再次去除上清液。其後,於殘渣中加入氯仿,浸漬一晩,將對殘渣浸漬液進行加壓過濾所獲得之固體於150℃下真空乾燥5小時,藉此以黃褐色粉末之形態獲得金屬有機結構體6-1。
[實施例6-2]
使用有機配位子2代替有機配位子1,除此以外,以與實施例6-1相同之操作,獲得金屬有機結構體6-2(淡綠色粉末)。
[實施例6-3]
使用有機配位子4代替有機配位子1,除此以外,以與實施例6-1相同之操作,獲得金屬有機結構體6-3(淡綠色粉末)。
[實施例7-1]
對有機配位子1(0.3 mmol)、氯化鋯(0.3 mmol)、水(3.6 mmol)、乙酸(9 mmol)、DMF 4 mL之溶液照射超音波。其後,將該溶液於120℃下加熱24小時。將反應液恢復至室溫後,進行離心分離10分鐘,去除上清液。於殘渣中加入DMF,再次進行離心分離10分鐘,去除上清液。將殘渣於DMF中浸漬一夜後,進行離心分離10分鐘,去除DMF。於殘渣中加入丙酮10 mL,將離心分離、去除上清液之操作重複3次,再次添加丙酮,浸漬一晩後,進行離心分離,將所獲得之固體於150℃下真空乾燥5小時,藉此以無色固體之形態獲得金屬有機結構體7-1。
[實施例7-2]~[實施例7-3]
利用下述表8所示之有機配位子進行反應,除此以外,進行與實施例7-1相同之操作,獲得金屬有機結構體7-2~7-3。將其結果示於表8。
[表8]
實施例 | 有機配位子 | 性狀 |
7-1 | 1 | 無色粉末 |
7-2 | 2 | 無色粉末 |
7-3 | 4 | 灰色粉末 |
[實施例7-4]
將氯化鋯、水、乙酸溶解於DMF並照射超音波,於室溫下靜置2天。其後添加有機配位子3之後,進行與實施例7-1相同之處理,獲得金屬有機結構體7-4(無色粉末)。
[實施例7-5]
除未添加水以外,進行與實施例7-4相同之操作,獲得金屬有機結構體7-5(無色粉末)。
[實施例7-6]~[實施例7-25]
以下述表9所示之有機配位子進行反應,除此以外,進行與實施例7-1相同之操作,獲得金屬有機結構體7-6~7-25。將其結果示於表9。
[表9]
實施例 | 有機配位子 | 加熱時攪拌 | 酸 | 性狀 |
7-6 | 2 | 無 | 苯甲酸 | 無色結晶 |
7-7 | 3 | 無 | 乙酸 | 無色粉末 |
7-8 | 3 | 有 | 乙酸 | 無色粉末 |
7-9 | 5 | 無 | 乙酸 | 無色粉末 |
7-10 | 6 | 無 | 乙酸 | 無色粉末 |
7-11 | 7 | 無 | 乙酸 | 無色粉末 |
7-12 | 8 | 無 | 乙酸 | 無色粉末 |
7-13 | 8 | 有 | 乙酸 | 無色粉末 |
7-14 | 9 | 無 | 乙酸 | 無色粉末 |
7-15 | 10 | 無 | 乙酸 | 無色粉末 |
7-16 | 11 | 無 | 乙酸 | 無色粉末 |
7-17 | 12 | 無 | 乙酸 | 灰色粉末 |
7-18 | 13 | 無 | 乙酸 | 無色粉末 |
7-19 | 15 | 無 | 乙酸 | 無色固體 |
7-20 | 16 | 無 | 乙酸 | 灰白色粉末 |
7-21 | 17 | 無 | 乙酸 | 無色固體 |
7-22 | 19 | 無 | 乙酸 | 無色固體 |
7-23 | 14 | 無 | 乙酸 | 無色固體 |
7-24 | 18 | 無 | 乙酸 | 無色固體 |
7-25 | 16 | 無 | 乙酸 | 無色固體 |
[實施例8-1]
對有機配位子1(0.175 mmol)、氯氧化鋯八水合物(0.175 mmol)、甲酸:DMF=1:7之混合溶劑4 mL之溶液照射超音波。其後,將該溶液於120℃下加熱24小時。將反應液恢復至室溫後,去除上清液。於殘渣中加入DMF,再次進行離心分離10分鐘,去除上清液,將該操作重複3次之後,添加DMF,浸漬一夜。自殘渣浸漬液去除DMF後,於殘渣中添加甲醇,將離心分離、去除上清液之操作重複3次。再次於殘渣中添加甲醇,浸漬一晩後,去除甲醇,將所獲得之固體於150℃下真空乾燥5小時,藉此以淺灰色粉末之形態獲得金屬有機結構體8-1。
[實施例9-1]
將有機配位子2(0.36 mmol)、四異丙醇鈦(0.074 mmol)、乙酸2.2 g、DMF7 mL進行混合並照射超音波。其後於120℃下加熱48小時。恢復至室溫後,進行離心分離10分鐘,去除上清液。於殘渣中加入DMF,再次進行離心分離10分鐘,去除上清液。於DMF中浸漬一夜後,進行離心分離10分鐘,去除DMF後,加入丙酮10 mL,將離心分離、去除上清液重複3次。再次加入丙酮,浸漬一晩之後,將離心分離之固體於150℃下真空乾燥5小時,藉此以灰白色粉末之形態獲得金屬有機結構體9-1。
[實施例9-2]~[實施例9-6]
以下述表10所示之有機配位子進行反應,除此以外,進行與實施9-1相同之操作,獲得金屬有機結構體9-2~9-6。將其結果示於表10。
[表10]
實施例 | 有機配位子 | 性狀 |
9-2 | 3 | 灰白色粉末 |
9-3 | 5 | 無色粉末 |
9-4 | 6 | 淡黃色粉末 |
9-5 | 10 | 淡黃色粉末 |
9-6 | 12 | 灰色粉末 |
[實施例10-1]
於有機配位子2(0.5 mmol)、氯化鉻六水合物(0.5 mmol)中添加DMF 5 mL,照射超音波。將該溶液於190℃下進行加熱24小時。恢復至室溫後,進行離心分離10分鐘,去除上清液。於殘渣中加入DMF 10 mL,再次進行離心分離10分鐘,去除上清液。於DMF中浸漬一夜之後,進行離心分離10分鐘,藉由加壓過濾去除DMF後,添加氯仿10 mL。將離心分離之固體於氯仿20 mL中浸漬一晩,再次進行離心分離,將該洗淨操作重複3次。其後,藉由將進行加壓過濾所獲得之固體於150℃下真空乾燥5小時,以綠色固體之形態獲得金屬有機結構體10-1。
[實施例10-2]~[實施例10-4]
以下述表11所示之有機配位子進行反應,除此以外,進行與實施例10-1相同之操作,獲得金屬有機結構體10-2~10-4。將其結果示於表11。
[表11]
實施例 | 有機配位子 | 加熱時間(hr) | 性狀 |
10-2 | 3 | 72 | 綠色固體 |
10-3 | 6 | 24 | 綠色固體 |
10-4 | 8 | 24 | 綠色固體 |
[實施例11-1]
於有機配位子2(0.18 mmol)、硝酸鋁九水合物(0.24 mmol)中添加DMF 5 mL,照射超音波。將該溶液於120℃下進行加熱24小時。恢復至室溫後,進行離心分離10分鐘,去除上清液。於殘渣中添加DMF 10 mL,再次進行離心分離10分鐘,去除上清液。於DMF中浸漬一夜之後,進行離心分離10分鐘,藉由加壓過濾去除DMF後,添加丙酮10 mL。將離心分離之固體於丙酮20 mL中浸漬一晩,再次進行離心分離,將該洗淨操作重複3次。其後,藉由將進行加壓過濾所獲得之固體於150℃下真空乾燥5小時,以無色粉末之形態獲得金屬有機結構體11-1。
[實施例11-2]~[實施例11-14]
以下述表12所示之有機配位子進行反應,除此以外,進行與實施例11-1相同之操作,獲得金屬有機結構體11-2~11-14。將其結果示於表12。
[表12]
實施例 | 有機配位子 | 加熱時間(hr) | 攪拌 | 溶劑 | 溫度(℃) | 性狀 |
11-2 | 3 | 24 | 無 | DMF | 120 | 無色粉末 |
11-3 | 5 | 24 | 無 | DMF | 120 | 無色粉末 |
11-4 | 6 | 24 | 無 | DMF | 120 | 無色粉末 |
11-5 | 8 | 24 | 無 | DMF | 120 | 無色粉末 |
11-6 | 8 | 42 | 無 | H2 O | 220 | 灰白色粉末 |
11-7 | 10 | 24 | 無 | DMF | 120 | 無色粉末 |
11-8 | 10 | 24 | 有 | DMF | 120 | 無色粉末 |
11-9 | 15 | 72 | 無 | DMF | 120 | 淡褐色固體 |
11-10 | 16 | 72 | 無 | DMF | 120 | 無色固體 |
11-11 | 17 | 72 | 無 | DMF | 120 | 無色固體 |
11-12 | 19 | 72 | 無 | DMF | 120 | 無色粉末 |
11-13 | 18 | 72 | 無 | DMF | 120 | 無色粉末 |
11-14 | 14 | 72 | 無 | DMF | 120 | 褐色粉末 |
[實施例12-1]
於有機配位子8(0.1 mmol)、氯化鐵(III)(0.25 mmol)中添加DMF 8 mL、乙酸1 mL,照射超音波。將該溶液於150℃下進行加熱168小時。恢復至室溫後,進行離心分離10分鐘,去除上清液。於殘渣中添加DMF 10 mL,再次進行離心分離10分鐘,去除上清液。於DMF中浸漬一夜之後,進行離心分離10分鐘,藉由加壓過濾去除DMF後,添加氯仿10 mL。將離心分離之固體於氯仿20 mL中浸漬一晩,再次進行離心分離,將該洗淨操作重複3次。其後,藉由將進行加壓過濾所獲得之固體於150℃下真空乾燥5小時,以褐色粉末之形態獲得金屬有機結構體12-1。
[實施例12-2]~[實施例12-4]
以下述表13所示之有機配位子進行反應,除此以外,進行與實施例12-1相同之操作,獲得金屬有機結構體12-2~12-4。將其結果示於表13。
[表13]
實施例 | 有機配位子 | 加熱時間(hr) | 金屬(當量) | 酸 | 性狀 |
12-2 | 8 | 168 | 硝酸鐵九水合物(1) | 乙酸 | 褐色粉末 |
12-3 | 10 | 18 | 氯化鐵六水合物(1) | TFA | 橙色粉末 |
12-4 | 10 | 18 | 氯化鐵六水合物(1/3) | TFA | 橙色粉末 |
[BET比表面積測定及儲氫量測定]
對所獲得之金屬有機結構體之一部分,測定BET比表面積及77 K-大氣壓下之儲氫量。
BET比表面積及77 K-大氣壓下之儲氫量之測定使用氣體吸附量測定裝置Tristar-II(Micromeritics公司製造)而進行。
BET比表面積按照如下方法算出。將50 mg左右之金屬有機結構體裝入玻璃槽內部。玻璃槽內部於135℃之溫度下減壓至真空,乾燥6小時。將玻璃槽安裝於氣體吸附量測定裝置,浸漬於裝有液態氮之恆溫槽中。緩慢增加玻璃槽中所含有之氮氣之壓力。進行測定直至導入至玻璃槽內部之氮氣之壓力成為1.0×105
Pa。
77 K常壓下之儲氫量按照如下方法算出。測定氮氣之後,將氣體種類變更為氫氣並進行測定。緩慢增加玻璃槽中所含有之氫氣之壓力。進行測定直至導入至玻璃槽內部之氫氣之壓力成為1.0×105
Pa。
將測得之BET比表面積及測得之77 K-大氣壓下之儲氫量之結果示於表14。表中之「-」意指未測定。
[表14]
有機金屬結構體編號 | BET比表面積(m2 /g) | 儲氫量(wt%) |
1-1 | 545 | - |
1-2 | 19.4 | - |
1-3 | 3.94 | - |
1-4 | 62.7 | - |
1-5 | 25 | - |
1-6 | 15.2 | - |
1-7 | 34 | - |
1-8 | 188 | - |
1-9 | 244 | - |
1-10 | 59 | - |
1-11 | 38.3 | - |
1-12 | 971 | 0.802 |
1-13 | 1 | 0.077 |
1-14 | 3 | 0.080 |
1-15 | 11 | 0.721 |
1-16 | 5 | 0.113 |
2-1 | 174 | 0.400 |
2-2 | 451 | 0.606 |
3-1 | 1256 | 0.933 |
3-2 | 1471 | 1.110 |
3-3 | 103 | 0.357 |
3-4 | 403 | 0.564 |
3-5 | 463 | 1.037 |
3-6 | 788 | 0.878 |
3-7 | 210 | 0.702 |
3-8 | 532 | 0.651 |
3-9 | 21 | 0.412 |
3-10 | 788 | 0.791 |
3-11 | 7 | 0.204 |
4-1 | 233 | 0.444 |
4-2 | 314 | 0.438 |
4-3 | 717 | 0.835 |
4-4 | 58 | 0.446 |
4-5 | 180 | 0.403 |
4-6 | 40 | 0.356 |
4-7 | 128 | 0.568 |
4-8 | 59 | 0.399 |
5-1 | 13.1 | 0.180 |
5-2 | 13.2 | 0.369 |
5-3 | 16.3 | 0.348 |
5-4 | 12.9 | 0.379 |
5-5 | 470 | 0.729 |
5-6 | 599 | 0.797 |
5-7 | - | 0.451 |
6-1 | 7.39 | 0.434 |
6-2 | 587 | 0.850 |
6-3 | 336 | 0.863 |
7-1 | 3014 | 1.482 |
7-2 | 2652 | 1.476 |
7-3 | 2592 | 1.549 |
7-4 | 2840 | 1.740 |
7-5 | 3046 | 1.707 |
7-6 | 2793 | 1.561 |
7-7 | 3038 | 1.860 |
7-8 | 2871 | 1.873 |
7-9 | 2146 | 1.830 |
7-10 | 3090 | 1.786 |
7-11 | 460 | 1.048 |
7-12 | 2628 | 1.889 |
7-13 | 2367 | 1.420 |
7-14 | 2480 | 1.540 |
7-15 | 2335 | 1.526 |
7-16 | 2603 | 1.420 |
7-17 | 3331 | 1.453 |
7-18 | 2854 | 1.159 |
7-19 | 939 | 0.837 |
7-20 | - | - |
7-21 | 1523 | 1.072 |
7-22 | 1070 | 1.168 |
7-23 | 621 | 0.688 |
7-24 | 198 | 0.438 |
7-25 | 425 | 1.050 |
8-1 | 3.09 | 0.235 |
9-1 | 818 | 0.632 |
9-2 | 858 | 0.710 |
9-3 | 593 | 0.709 |
9-4 | 1030 | 0.726 |
9-5 | 787 | 0.549 |
9-6 | 1038 | 0.686 |
10-1 | 563 | 0.651 |
10-2 | 582 | 0.802 |
10-3 | 428 | 0.643 |
10-4 | 2 | 0.031 |
11-1 | 1140 | 0.984 |
11-2 | 1557 | 1.367 |
11-3 | 1343 | 1.405 |
11-4 | 924 | 1.054 |
11-5 | 1018 | 1.041 |
11-6 | 129 | 0.464 |
11-7 | 1545 | 1.227 |
11-8 | 1602 | 1.145 |
11-9 | 946 | 0.880 |
11-10 | 677 | 0.576 |
11-11 | 1168 | 1.190 |
11-12 | 791 | 0.693 |
11-13 | 708 | 0.831 |
11-14 | 447 | 0.659 |
12-1 | - | 0.243 |
12-2 | - | 0.534 |
12-3 | 13 | 0.172 |
12-4 | 28 | 0.202 |
[單晶X射線結構解析]
按照以下所示之測定條件分別對實施例1-2及2-2中所獲得之金屬有機結構體1-2、2-2進行X射線結構解析。
[測定條件]
於顯微載片載置一粒實施例1-2中所獲得之金屬有機結構體1-2之0.1×0.05×0.05 mm之無色透明之單晶,使用單晶X射線解析裝置(D8VENTURE,Bruker公司製造),對單晶照射0.78192 Å之波長之X射線,藉此獲取繞射資料。
對所獲得之繞射資料進行解析,決定結構。將其結果示於表15。
[表15]
測定溫度/℃ | -173℃ |
結晶尺寸/mm | 0.10×0.05×0.05 |
結晶顏色 | 無色 |
化學式 | C15 H8.5 N0. 5 O3 Zn0. 75 |
分子量 | 292.75 |
晶系 | 單斜晶系(Monoclinic) |
空間群 | I2/m |
a/Å | 6.0704(4) |
b/Å | 27.533(2) |
c/Å | 26.3841(19) |
α/° | 90 |
β/° | 88.881(6) |
γ/° | 90 |
V/Å3 | 4408.9(5) |
Z | 8 |
收集到之反射點 | 19832 |
獨立反射點 | 5078 |
以與上述所示之測定相同之條件對實施例2-2中所獲得之金屬有機結構體2-2進行X射線結構解析。將其結果示於表16。
[表16]
[產業上之可利用性]
測定溫度/℃ | -173℃ |
結晶尺寸/mm | 0. 02×0. 01×0.01 |
結晶顏色 | 無色 |
化學式 | C40 H26 N3 O5 Zn |
分子量 | 694.01 |
晶系 | 單斜晶系(Monoclinic) |
空間群 | C2/c |
a/Å | 25.493(15) |
b/Å | 28.775(17) |
c/Å | 9.384(6) |
β/° | 96.999(7) |
V/Å3 | 6832(7) |
Z | 8 |
收集到之反射點 | 76628 |
獨立反射點 | 7836 |
本發明之金屬有機結構體能夠以實用性水準儲藏氫氣等氣體。其結果,例如隨著氫社會之到來,氫之利用將變得更加容易。
Claims (3)
- 如請求項1之金屬有機結構體,其進而包含除式(V)所表示之羧酸離子以外之有機配位子作為構成成分。
- 一種氫氣儲藏方法,其具有如下步驟:使氫氣與如請求項1或2之金屬有機結構體接觸,將上述氫氣吸附或吸藏於上述金屬有機結構體之內部。
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