TWI599569B - 銥錯合物之製造方法 - Google Patents
銥錯合物之製造方法 Download PDFInfo
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- TWI599569B TWI599569B TW104130301A TW104130301A TWI599569B TW I599569 B TWI599569 B TW I599569B TW 104130301 A TW104130301 A TW 104130301A TW 104130301 A TW104130301 A TW 104130301A TW I599569 B TWI599569 B TW I599569B
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- Taiwan
- Prior art keywords
- ruthenium
- diketone
- solution
- treatment
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 36
- 229910052741 iridium Inorganic materials 0.000 title description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 96
- 238000011282 treatment Methods 0.000 claims description 89
- 239000003513 alkali Substances 0.000 claims description 68
- -1 hydrazine compound Chemical class 0.000 claims description 54
- 238000010306 acid treatment Methods 0.000 claims description 50
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 45
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 43
- 229910052707 ruthenium Inorganic materials 0.000 claims description 43
- 239000007983 Tris buffer Substances 0.000 claims description 38
- 230000004913 activation Effects 0.000 claims description 32
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 28
- 239000002585 base Substances 0.000 claims description 22
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000002923 oximes Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Chemical group 0.000 claims description 2
- 239000012327 Ruthenium complex Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SBRYTXXHTKCMFT-UHFFFAOYSA-N 1,1,1-trifluorohexane-2,4-dione Chemical compound CCC(=O)CC(=O)C(F)(F)F SBRYTXXHTKCMFT-UHFFFAOYSA-N 0.000 description 3
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012982 x-ray structure analysis Methods 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001308 synthesis method 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
- 238000004809 thin layer chromatography Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WPSIMNJSPMMFLU-UHFFFAOYSA-N N,N,N',2,2,2-hexafluoroethanimidamide Chemical class FN(C(C(F)(F)F)=NF)F WPSIMNJSPMMFLU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MXHJYCDSUGIACP-UHFFFAOYSA-N propan-2-one;1,1,1-trifluoropropan-2-one Chemical compound CC(C)=O.CC(=O)C(F)(F)F MXHJYCDSUGIACP-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
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Description
本發明係有關製造β-二酮配位於銥之銥錯合物的三(β-二酮鹽)銥之方法。更詳細為,係有關可將廣泛種類之β-二酮被配位於銥而合成銥錯合物之方法。
β-二酮配位於銥所形成之三(β-二酮鹽)銥已知為,所謂CVD法(化學氣相蒸鍍法)、ALD法(原子層蒸鍍法)之化學蒸鍍法所使用的原料化合物(前體(precursor))。例如專利文獻1、2所記載,由銥錯合物之三(5-甲基-2,4-己烷二酮酸)銥或三(2,4-辛烷二酮鹽)銥所形成之形成銥薄膜用的化學蒸鍍用之原料化合物。
又,近年來有關有機電解發光(EL)元件及有機電氣化學發光(ECL)元件等有機發光元件用之磷光材料曾檢討使用,銥環狀配位多座配位基所得之環金屬化銥錯合物(專利文獻3)。又,三(β-二酮鹽)銥適用為製造環金屬化銥錯合物等有機發光元件用之磷光材料用的
原料(中間原料)。例如非專利文獻1所揭示,以三(2,4-戊烷二銅鹽)銥為原料,藉由使2-苯基吡啶(ppy)等之芳香族雜環雙座配位基反應,製造由環金屬化銥所形成之有機發光元件用的磷光材料之方法。
已知的三(β-二酮鹽)銥之製造方法如,以三氯化銥等之銥鹽為開始原料,加入配位基用之β-二酮後,加入碳酸氫鉀等成為鹼性進行反應之步驟(專利文獻4)。
該先前之合成法可直接合成上述三(5-甲基-2,4-己烷二酮鹽)銥、三(2,4-辛烷二酮鹽)銥及三(2,4-戊烷二酮鹽)銥。但經本發明者們檢討後確認,配位廣泛範圍之β-二酮以製造銥錯合物時,以先前合成方法係難進行反應。
例如有關上述作為磷光材料用之環金屬化銥錯合物需檢討配位目的為提升發光效率之各種配位基的錯合物。為了得到該類環金屬銥錯合物之開始原料,本申請發明者們曾嘗試配位具有含有氟等氫、碳以外之元素,及環狀烴等之各種結構的β-二酮以合成銥錯合物,但先前方法中無法進行合成反應而無法得到目的之三(β-二酮鹽)銥。
[專利文獻1]特許第4054215號說明書
[專利文獻2]特許第4856825號說明書
[專利文獻3]特開2012-6914號公報
[專利文獻4]特開平7-316176號公報
非專利文獻1:Inorg. Chem., 30卷,1685頁,1991年
因此本發明係提供三(β-二酮鹽)銥之製造方法中,未限定配位用之β-二酮的範圍下可進行合成反應之方法。
本發明之課題的要點為,一般合成方法中銥化合物相對於一定範圍外之β-二酮係無法完全具有反應性。相對該課題經本發明者們專心檢討後發現,相對於開始原料用之銥化合物進行一定活性化處理,而使銥化合物活性化後,即使相對於上述β-二酮也可得反應性,合成目的之三(β-二酮鹽)銥。
即,本發明為一種三(β-二酮鹽)銥之製造方法,其特徵為,使銥化合物與化1所表示之β-二酮反應,使前述β-二酮配位於銥而製造化2所表示之三(β-二
酮鹽)銥的方法中,對前述銥化合物進行包含下述(a)鹼處理與(b)酸處理之活性化處理而使銥化合物活性化後,使β-二酮反應。
(a)鹼處理:將鹼加入前述銥化合物之溶液中,使溶液之pH比添加前更偏向鹼側,且使pH為10以上之處理。
(b)酸處理:將酸加入經前述鹼處理後之前述溶液中,使溶液之pH比酸添加前更偏向酸性側,且使酸添加前後之溶液的pH差為0.1以上10以下之處理。
下面將詳細說明本發明有關之銥錯合物(三(β-二酮鹽)銥)之製造方法中的各步驟之內容。
本發明中作為開始原料用之銥化合物適用廣泛範圍之銥化合物。例如適用銥之硝酸鹽、硫酸鹽、氫氧化物、鹵化物等。更具體為,適用硝酸銥、硫酸銥、氫氧化銥、六氯銥酸銨、氯化銥、氯化銥酸、氯化銥酸鉀、氯化銥酸鈉、溴化銥、溴化銥酸、溴化銥酸鉀、溴化銥酸鈉、碘化銥、氧化銥等。該等銥化合物之銥的價數可為3價或4價。
但考量最終三(β-二酮鹽)銥之產率,銥化合物較佳為硝酸銥(III、IV)、氯化銥(III、IV)、六氯銥酸銨(III、IV)。該等銥化合物中銥與陰離子之鍵結較弱。因進行三(β-二酮鹽)銥之合成反應時,需同時進行使開始原料之銥化合物分解,與由β-二酮進行主脫質子化之共軛鹼,故使用上述較佳之銥化合物可有效率合成錯合物。
銥化合物係以溶液狀態供給反應。銥化合物
溶液之溶劑較佳為水。溶液之銥化合物濃度較佳為0.01mol/L以上20mol/L以下。又,該銥化合物之溶液的pH多半為0以上12以下之範圍內。
其次本發明中係對上述銥化合物之溶液進行包含鹼處理與酸處理之活性化處理。該等處理為,具有使銥化合物為活性化之狀態,再進行三(β-二酮鹽)銥之合成反應的作用。
鹼處理為,將鹼加入銥化合物之溶液中,使其pH比鹼添加前更偏向鹼側,且使pH為10以上之處理。鹼處理更佳為,使銥化合物之溶液pH為12以上。此時所添加之鹼較佳為,氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化銫、氫氧化鋇、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、氨、氫氧化四甲基銨。鹼較佳以溶液狀態添加,鹼溶液之濃度較佳為0.01mol/L以上20mol/L以下。進行鹼處理後之銥化合物溶液較佳為,以上述pH範圍靜置0.5小時以上24小時以下再進行其次之處理(酸處理)。又,鹼處理中係使銥化合物溶液之pH位移至鹼側,但該處理之鹼添加前後的pH差較佳為2以上13以下,更佳為設定5以上13以下之pH差。
鹼處理後其次進行之酸處理為,將酸加入鹼領域中之銥化合物溶液中,使pH比酸添加前更偏向酸性側且使酸添加前後之pH差為0.1以上10以下之處理。此時所添加之酸較佳為,硝酸、鹽酸、溴化氫酸、碘化氫酸、次氯酸、亞氯酸、氯酸、過氯酸、磷酸、硫酸、六氟
銻酸、四氟硼酸、六氟磷酸、鉻酸、硼酸、甲烷磺酸、乙烷磺酸、苯磺酸、p-甲苯磺酸、三氟甲烷磺酸、乙酸、檸檬酸、甲酸、葡糖酸、乳酸、草酸、酒石酸。所添加之酸溶液的酸濃度較佳為0.01mol/L以上20mol/L以下。又,該酸處理較佳為,使酸添加前後之pH差為1以上10以下。
藉由上述所說明的包含鹼處理與酸處理之活性化處理而使銥化合物活性化。該銥化合物之活性化係被發現於經鹼處理與酸處理雙方後之階段。又,鹼處理與酸處理之順序為先進行鹼處理。又,鹼處理與酸處理均可於室溫下進行。具體上活性化處理可於0℃以上50℃以下進行。
活性化處理後之銥化合物係與β-二酮反應進行錯合物合成。此時進行反應之β-二酮為,配位於製造目的之銥錯合物中銥之β-二酮,即上述化1之式所表示的β-二酮。
化1之式中β-二酮之Ra及Rb為,烴基或烴基之氫原子被鹵原子取代的取代基。Ra及/或Rb為烴基時較佳為脂肪族烴基或芳香族烴基。又,較佳為該等烴基之氫原子被鹵原子取代之物。
更具體為,Ra及/或Rb為脂肪族烴基時較佳為直鏈狀或支鏈狀之烴基。又以碳數1~10之脂肪族烴基為佳。例如烷基(更佳為碳數1~5)、環烷基、新戊基。更具體如,甲基、乙基、丙基、異丙基、n-丁基、t-
丁基、n-辛基、n-癸基、n-十六烷基、環丙基、環戊基、環己基、新戊基等。又,較佳為該等脂肪族烴基中之氫原子被氟取代之物。該Ra與Rb可為相異之取代基或相同之取代基。
Ra及/或Rb為芳香族烴基時較佳為碳數6~20之芳香族烴基。更佳為碳數6~10之芳香族烴基。具體如,苯基、萘基、聯苯基、芴基、菲基、蒽基、三苯并苯基、聯三苯基、芘基、基、甲苯基、二甲苯基、薁基、苊基、茚基等。又,較佳為該等芳香族烴基中之氫原子被氟取代之物。該Ra與Rb可為相異之取代基或相同之取代基。
又,Rc為由氫原子、鹵原子、烴基中任一種所形成之取代基。Rc之取代基為鹵原子時特佳為氟原子。Rc為烴基時較佳為直鏈狀或支鏈狀之烴基。又以碳數1~10之脂肪族烴基為佳。例如烷基(更佳為碳數1~5)、環烷基、新戊基。更具體如,甲基、乙基、丙基、異丙基、n-丁基、t-丁基、n-辛基、n-癸基、n-十六烷基、環丙基、環戊基、環己基、新戊基等。又,較佳為該等脂肪族烴基中之氫原子被氟取代之物。
考量上述之β-二酮的具體例,可使下述般β-二酮反應。
此時使活性化後之銥化合物與β-二酮反應的具體方法為,將β-二酮加入銥化合物溶液中。將該β-二酮加入銥化合物溶液的時間可為,將β-二酮加入活性化處理結束後之銥化合物溶液中,但也可於活性化處理結束前將β-二酮加入銥化合物溶液中,再進行活性化處理。
將β-二酮加入活性化處理結束後之銥化合物溶液時,可直接將活性化處理後之溶液供給合成反應。但會因原料化合物之種類而藉由活性化處理生成析出物時,可過濾回收析出物再分散於水中,其後加入β-二酮。藉此將β-二酮加入活性化處理後之溶液或析出物之分散液中,可進行三(β-二酮鹽)銥之合成反應。
又,將β-二酮加入活性化處理結束前之銥化合物溶液的技術性意義係包括,進行鹼處理及酸處理雙方前預先將β-二酮加入銥化合物溶液中,及於活性化處理之途中階段添加,即於鹼處理與酸處理之中間將β-二酮加入銥化合物溶液中雙方。
將β-二酮加入活性化處理結束前之銥化合物溶液時,於添加β-二酮之階段係不會進行三(β-二酮鹽)銥之合成反應,而係於結束活性化處理之酸處理後才開始合成反應。
如上述將β-二酮加入銥化合物溶液之三種模式被容許的理由為,為了進行三(β-二酮鹽)銥之合成反應需使銥化合物活性化,及銥化合物的活性化可於藉由結束鹼處理與酸處理雙方後發現。
又,考量上述所說明之三種β-二酮的添加時間,作為活性化處理時添加鹼、酸時之pH調整基準的「鹼(酸)添加前之溶液」係指,如文字所示的添加鹼(酸)之前的溶液。即,於銥化合物之活性化處理結束後加入β-二酮時,鹼添加前之「溶液」為銥化合物溶液。另外進行活性化處理(鹼處理)前預先將β-二酮加入銥化合物溶液時,鹼添加前之「溶液」為銥化合物溶液與β-二酮之混合溶液。又,於鹼處理與酸處理之中間過程中將β-二酮加入銥化合物溶液時,鹼添加前之「溶液」雖僅為銥化合物溶液,但酸添加前之「溶液」為銥化合物溶液與β-二酮之混合溶液。
又,將β-二酮加入銥化合物溶液時可能因其種類而改變銥化合物溶液之pH(多半係不會改變)。銥化合物溶液與β-二酮之混合溶液為上述鹼(酸)添加前之溶液時,該溶液之pH係採用混合溶液狀態下之值。又,藉由上述添加鹼(酸)而算出較佳pH差之基準也相同。
又,銥化合物與β-二酮之反應條件中,β-二酮之添加量可為,比製造目的之銥錯合物的當量數(相對於銥為3當量)多。較佳為相對於銥添加3當量以上20當量以下。
為了使結束活性化處理後含有β-二酮之銥化合物溶液更有效率進行三(β-二酮鹽)銥之合成反應,可將溶液加熱。活性化處理可於室溫下進行,但將溫度加熱至室溫以上時,可提升三(β-二酮鹽)銥之合成反應的產
率。此時之反應溫度較佳為維持於50℃以上100℃以下。反應時間較佳為0.5小時以上24小時以下。
錯合物合成反應後析出反應液中所生成之銥錯合物。即將其固液分離後洗淨固體成分再精製,可得高純度之三(β-二酮鹽)銥。
如上述所說明,本發明之三(β-二酮鹽)銥的製造方法為,可使廣泛種類之β-二酮配位於銥。藉此可增加製造具有多樣特性之三(β-二酮鹽)銥的可能性,作為開發適用為有機電解發光元件等之磷光材料或薄膜形成原料之物用的基礎。
下面將說明本發明之較佳的實施形態。如上述本發明之三(β-二酮鹽)銥之製造方法中,對銥化合物之溶液添加β-二酮之時間為,(1)將β-二酮加入活性化處理結束後之銥化合物溶液的方法,(2)進行鹼處理及酸處理雙方之前預先將β-二酮加入銥化合物溶液的方法,(3)於活性化處理之途中(鹼處理或酸處理之中間階段)將β-二酮加入銥化合物溶液的方法之三種模式。本實施形態係基於該(1)~(3)之方法製造銥錯合物。
第一實施形態:本實施形態係以上述(1)之
方法製造銥錯合物。其中開始原料之銥化合物係使用硝酸銥(III)Ir(NO3)3,使其與作為β-二酮用之1,1,1,6,6,6-六氟-2,4-戊二酮(別名:六氟乙醯丙酮)反應,製造三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥(三(六氟乙醯丙酮鹽)銥)。
準備濃度9.1wt%之硝酸銥20.26g(銥含量1.84g,9.6mmol)添加蒸餾水18.8mL所得之硝酸銥溶液。該硝酸銥溶液為深藍色之水溶液,pH為0.7。
對該硝酸銥溶液進行活性化處理之鹼處理及酸處理。鹼處理中係添加1N之氫氧化鈉溶液。鹼處理係使鹼添加前之硝酸銥溶液的pH(0.7)偏向鹼側。本實施形態中調整鹼添加量可形成pH不同之溶液。添加鹼後係將硝酸銥溶液靜置於室溫下1小時。
其次該溶液之酸處理係添加6%稀硝酸。酸處理也可藉由調整酸添加量而使pH不同。又,以上述之鹼處理及酸處理中,溶液之外觀不會產生大變化,為深藍色之水溶液。
將19.5g,59.2mmol之1,1,1,6,6,6-六氟-2,4-戊二酮加入結束上述鹼處理及酸處理之活性化處理後的硝酸銥溶液中。該添加量相對於銥1mol相當為6當量。添加1,1,1,6,6,6-六氟-2,4-戊二酮後,將溶液加熱至55℃並保持2.5小時進行反應。
反應後之反應液為暗黃色之懸浮液。反應液之pH係若干偏向酸性側。過濾該反應液進行固液分離後,洗淨固體成分再管柱精製(溶劑為己烷:乙酸乙酯=5:1)回收三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥。
藉由1H NMR(質子核磁共振)及X線結構解析以分析合成後回收之銥錯合物。此時1H NMR係藉由1H NMR裝置(400MHz)進行分析,及使用測定溶劑CDCl3確認。又,X線結構解析之方法為,藉由單結晶X線結構解析裝置(VariMax with RAPID)進行分析。併用1H NMR與X線結構解析之理由為,僅藉由1H NMR分析配位對稱β-二酮之1,1,1,6,6,6-六氟-2,4-戊二酮所得的三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥尚且不足。又,藉由該等分析結果確認此次製造之銥錯合物為,三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥。又,確認的同時算出回收之銥錯合物的產率(由銥量算出)。
本實施形態中除了進行上述鹼處理及酸處理之試驗例外,也嘗試依據未進行鹼處理及酸處理之先前的方法合成銥錯合物。另外也檢討未進行酸處理而僅進行鹼處理之情形。
本實施形態中對銥化合物溶液之鹼處理、酸處理、添加β-二酮之各階段進行pH測定。該pH測定方法為,將pH複合電極(直接讀取溫度傳感器被一體化之玻璃電極與比較電極的電位差)浸漬於pH6.86、pH4.01、pH9.18三種標準液中,進行3點校正後測定。
本實施形態中三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥合成試驗之結果的鹼處理、酸處理、添加β-二酮後之pH值、產率如表1所示。
由表1得知,藉由組合鹼處理與酸處理之活性化處理可合成三(1,1,1,6,6,6-六氟-2,4-戊二酮鹽)銥
(實施例1~實施例8)。又得知,該活性化處理中鹼處理及酮處理於處理時存在適當之pH。即,鹼處理時藉由添加鹼使pH偏向鹼側的同時需使pH為10以上,但未具備該要件之比較例2、3無法確認合成銥錯合物。又,即使酸處理中非單使溶液位移至酸性側,pH差也需為0.1以上10以下,但未具備該要件之比較例1無法確認合成。另外未進行鹼處理與酸處理之比較例4,及僅進行鹼處理之比較例5無法確認合成銥錯合物。又,該等未確認合成銥錯合物之試驗例中,溶液未發現變化,且即使該溶液進行薄層色譜分析(TLC)也無法觀察到目的物。
第2實施形態:本實施形態係以上述(2)之方法製造銥錯合物。其中開始原料之銥化合物係使用氯化銥(III)(IrCl3‧nH2O),使其與作為β-二酮用之1,1,1-三氟-2,4-己二酮反應,製造三(1,1,1-三氟-2,4-己二酮鹽)銥。
本實施形態為,預先將β-二酮加入銥化合物溶液中,再進行活性化處理之方法。首先準備氯化銥
10.0g(銥含量5.2g)添加蒸餾水94mL所得之氯化銥溶液。其次加入25.9g、168.1mmol之1,1,1-三氟-2,4-己二酮。其添加量相對於銥1mol相當於6當量。又,1,1,1-三氟-2,4-己二酮加入氯化銥溶液時溶液之外觀上未出現變化,確認為未發生反應。
其次對該混合溶液進行鹼處理及酸處理。本實施形態中,鹼處理係使用1N之碳酸鈉溶液。又,酸處理係使用6%乙酸。活性化處理之方法基本上與第1實施形態相同。
結束鹼處理及酸處理後,將混合溶液加熱至55℃並保持2.5小時進行反應。反應後之溶液為暗黃色之懸浮液。過濾該反應液進行固液分離後,洗淨固體成分,再管柱精製回收三(1,1,1-三氟-2,4-己二酮鹽)銥。藉由1H NMR分析合成所得之銥錯合物,結果確認為(1,1,1-三氟-2,4-己二酮鹽)銥。其後算出銥錯合物之產率。
又,本實施形態也同時檢討未進行鹼處理及酸處理之方法,及僅進行酸處理之情形。本實施形態中三(1,1,1-三氟-2,4-己二酮鹽)銥合成試驗之結果的鹼處理、酸處理、β-二酮添加後之pH值、產率同如表2所示。又,本實施形態之各階段的pH測定方法、1H NMR之方法與第1實施形態相同。
即使反應前銥化合物溶液添加β二酮類,仍可確認藉由活性化處理可合成銥錯合物(實施例9~實施例16)。又得知,鹼處理、酸處理之必要性,及各處理之較佳pH範圍及pH差也傾向與第1實施形態相同。又,本實施形態中曾嘗試僅進行酸處理之方法,但無法合成錯合物(比較例10)。
第3實施形態:本實施形態係以上述(3)之方法製造銥錯合物。其中開始原料之銥化合物係使用六氯銥酸銨(III)((NH4)3[IrCl6]),使其與作為β-二酮用之1,1,1-三氟-2,4-戊二酮(1,1,1-三氟乙醯丙酮)反應,製造三(1,1,1-三氟-2,4-戊二酮鹽)銥(三(1,1,1-三氟乙醯丙
酮鹽)銥)。
該實施形態為,對六氯銥酸銨溶液進行鹼處理後加入1,1,1-三氟-2,4-戊二酮,其後再進行酸處理之方法。
首先準備六氯銥酸銨10.05g(銥含量4.06g、21.1mmol)添加蒸餾水470mL所得之六氯銥酸銨溶液。其次對該六氯銥酸銨溶液進行鹼處理。鹼處理係添加1N之氫氧化鉀溶液。添加鹼後,將六氯銥酸銨溶液靜置於室溫下1小時。
將25.9g、168.1mmol之1,1,1-三氟-2,4-戊二酮加入經鹼處理後之六氯銥酸銨溶液中。其添加量相對於銥1mol相當於6當量。
其次對該溶液進行酸處理。酸處理係使用6%磷酸。藉由酸處理調整pH時,係以六氯銥酸銨溶液與1,1,1-三氟-2,4-戊二酮鹽之混合溶液作為調整前之溶液用,以其pH為基準下使其成為酸性側之值。酸處理後將溶液加熱至55℃並保持2.5小時進行反應。
反應後之反應液為暗黃色之懸浮液。過濾該反應液進行固液分離後,洗淨固體成分,再管柱精製(溶劑為己烷:乙酸乙酯=5:1)回收三(1,1,1-三氟-2,4-戊二酮鹽)銥。藉由1H NMR分析合成所得之銥錯合物,結果確認為三(1,1,1-三氟-2,4-戊二酮鹽)銥。其後算出產率。
又,本實施形態也同時檢討未進行鹼處理及酸處理之方法,及僅進行酸處理之情形。本實施形態之三(1,1,1-三氟-2,4-戊二酮鹽)銥合成試驗之結果的鹼處理、酸處理、β-二酮添加後之pH值、產率同如表3所示。又,本實施形態之各階段的pH測定方法、1H NMR之方法與第1實施形態相同。
即使鹼處理與酸處理之間,即活性化處理之途中添加β-二酮時,進行酸處理而結束活性化處理後仍可確認合成銥錯合物(實施例17~實施例24)。又,確認該方法中藉由鹼處理、酸處理之pH範圍、pH差得知可否合成錯合物。
藉由上述所說明之本發明可將廣泛種類之β-二酮配位於銥。本發明之方法適用為CVD法及ALD法等之化學蒸鍍用原料化合物的製造方法,又,適用為有機EL元件、有機ECL元件等之有機發光元件用磷光材料之
原料(中間原料)的製造方法。本發明適用為增廣各種用途中製造三(β-二酮鹽)銥之可能性的方法。
Claims (4)
- 一種三(β-二酮鹽)銥之製造方法,其特徵為,使銥化合物與化1所表示之β-二酮反應,製造前述β-二酮配位於銥所得之化2所表示之三(β-二酮鹽)銥的方法中,對前述銥化合物進行包含下述(a)鹼處理與(b)酸處理之活性化處理而使銥化合物活性化後,再與β-二酮反應,(a)鹼處理:將鹼加入前述銥化合物之溶液中,使溶液之pH比鹼添加前更偏向鹼側,且pH為10以上之處理,(b)酸處理:將酸加入經前述鹼處理後之前述溶液中,使溶液之pH比酸添加前更偏向酸性側,且酸添加前後之溶液的pH差為0.1以上10以下之處理,
- 如請求項1之三(β-二酮鹽)銥之製造方法,其中鹼處理(a)中鹼添加後之pH為12以上。
- 如請求項1或2之三(β-二酮鹽)銥之製造方法,其中鹼處理(a)中鹼添加前後之溶液的pH差為2以上13以下。
- 如請求項1或2之三(β-二酮鹽)銥之製造方法,其中酸處理(b)中酸添加前後之溶液的pH差為1以上10以下。
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