TWI546309B - 含雙(三牙配基)的銥金屬錯合物 - Google Patents
含雙(三牙配基)的銥金屬錯合物 Download PDFInfo
- Publication number
- TWI546309B TWI546309B TW103144964A TW103144964A TWI546309B TW I546309 B TWI546309 B TW I546309B TW 103144964 A TW103144964 A TW 103144964A TW 103144964 A TW103144964 A TW 103144964A TW I546309 B TWI546309 B TW I546309B
- Authority
- TW
- Taiwan
- Prior art keywords
- bis
- tridentate
- mmol
- hexane
- metal complex
- Prior art date
Links
- 239000003446 ligand Substances 0.000 title description 6
- 150000002503 iridium Chemical class 0.000 title 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- -1 dimethylamino, diphenylamino Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 98
- 230000015572 biosynthetic process Effects 0.000 description 74
- 238000003786 synthesis reaction Methods 0.000 description 74
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 70
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 65
- 238000005481 NMR spectroscopy Methods 0.000 description 41
- 239000000203 mixture Substances 0.000 description 26
- 235000019439 ethyl acetate Nutrition 0.000 description 25
- 239000007787 solid Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 230000003595 spectral effect Effects 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 239000000539 dimer Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000010953 base metal Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229960004132 diethyl ether Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WXRFPTPIIVUOLC-UHFFFAOYSA-N 2-(2,4-difluoro-5-pyridin-2-ylphenyl)pyridine Chemical compound FC1=CC(F)=C(C=2N=CC=CC=2)C=C1C1=CC=CC=N1 WXRFPTPIIVUOLC-UHFFFAOYSA-N 0.000 description 3
- FMJXSSNLLMLZAR-UHFFFAOYSA-N 2-(3-tert-butyl-5-pyridin-2-ylphenyl)pyridine Chemical compound C=1C(C(C)(C)C)=CC(C=2N=CC=CC=2)=CC=1C1=CC=CC=N1 FMJXSSNLLMLZAR-UHFFFAOYSA-N 0.000 description 3
- ZZASYICXYVXBAG-UHFFFAOYSA-N 2-[4-(trifluoromethyl)phenyl]-6-[5-(trifluoromethyl)-1H-pyrazol-3-yl]pyridine Chemical compound FC(C1=NNC(=C1)C1=NC(=CC=C1)C1=CC=C(C=C1)C(F)(F)F)(F)F ZZASYICXYVXBAG-UHFFFAOYSA-N 0.000 description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- PPUZKAPOPPRMFE-UHFFFAOYSA-N 1,5-dibromo-2,4-difluorobenzene Chemical compound FC1=CC(F)=C(Br)C=C1Br PPUZKAPOPPRMFE-UHFFFAOYSA-N 0.000 description 2
- ILBMTZXHVSOMTE-UHFFFAOYSA-N 1-[6-[4-(trifluoromethyl)phenyl]pyridin-2-yl]ethanone Chemical compound FC(C1=CC=C(C=C1)C1=CC=CC(=N1)C(C)=O)(F)F ILBMTZXHVSOMTE-UHFFFAOYSA-N 0.000 description 2
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 125000006663 (C1-C6) perfluoroalkyl group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- SSPNOMJZVHXOII-UHFFFAOYSA-N 1,3-dibromo-5-tert-butylbenzene Chemical compound CC(C)(C)C1=CC(Br)=CC(Br)=C1 SSPNOMJZVHXOII-UHFFFAOYSA-N 0.000 description 1
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- RUJTWTUYVOEEFW-UHFFFAOYSA-N 1-(6-bromopyridin-2-yl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=N1 RUJTWTUYVOEEFW-UHFFFAOYSA-N 0.000 description 1
- SDIJZFDKSOZOPC-UHFFFAOYSA-N 1-[6-(4-tert-butylphenyl)pyridin-2-yl]ethanone Chemical compound C(C)(C)(C)C1=CC=C(C=C1)C1=CC=CC(=N1)C(C)=O SDIJZFDKSOZOPC-UHFFFAOYSA-N 0.000 description 1
- MGHBDQZXPCTTIH-UHFFFAOYSA-N 1-bromo-2,4-difluorobenzene Chemical compound FC1=CC=C(Br)C(F)=C1 MGHBDQZXPCTTIH-UHFFFAOYSA-N 0.000 description 1
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 description 1
- MSQCQINLJMEVNJ-UHFFFAOYSA-N 1-chloroisoquinoline Chemical compound C1=CC=C2C(Cl)=NC=CC2=C1 MSQCQINLJMEVNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- SURCGQGDUADKBL-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-5-nitrobenzo[de]isoquinoline-1,3-dione Chemical class [O-][N+](=O)C1=CC(C(N(NCCO)C2=O)=O)=C3C2=CC=CC3=C1 SURCGQGDUADKBL-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- UHXCQHKVCXFVEE-UHFFFAOYSA-N 2-(5-tert-butyl-1H-pyrazol-3-yl)-6-[4-(trifluoromethyl)phenyl]pyridine Chemical compound C(C)(C)(C)C1=NNC(=C1)C1=NC(=CC=C1)C1=CC=C(C=C1)C(F)(F)F UHXCQHKVCXFVEE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- YLYPIBBGWLKELC-RMKNXTFCSA-N 2-[2-[(e)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methylpyran-4-ylidene]propanedinitrile Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=CC(=C(C#N)C#N)C=C(C)O1 YLYPIBBGWLKELC-RMKNXTFCSA-N 0.000 description 1
- JOACEYFXFYWUIK-UHFFFAOYSA-N 2-bromo-4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC(Br)=C1 JOACEYFXFYWUIK-UHFFFAOYSA-N 0.000 description 1
- QDDILSIJVYYDCY-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO.CCOCCO QDDILSIJVYYDCY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 1
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 1
- CMFQXPIZAKBRCG-UHFFFAOYSA-N 4-tert-butyl-1-oxidopyridin-1-ium Chemical compound CC(C)(C)C1=CC=[N+]([O-])C=C1 CMFQXPIZAKBRCG-UHFFFAOYSA-N 0.000 description 1
- UGGNULHQVUWRGQ-UHFFFAOYSA-N 4-tert-butyl-2-chloropyridine Chemical compound CC(C)(C)C1=CC=NC(Cl)=C1 UGGNULHQVUWRGQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000012267 brine Substances 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
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- KDLHZDBZIXYQEI-VENIDDJXSA-N palladium-100 Chemical compound [100Pd] KDLHZDBZIXYQEI-VENIDDJXSA-N 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- GYUURHMITDQTRU-UHFFFAOYSA-N tributyl(pyridin-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CC=N1 GYUURHMITDQTRU-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
本發明是有關於一種用於有機發光二極體的發光層中的銥金屬錯合物,特別是指一種含雙(三牙配基)的銥金屬錯合物。
Andrew J.Wilkinson等人在2006年Inorg.Chem.期刊發表的「Luminescent Complexes of Iridium(III)Containing N^C^N-Coordinating Tridentate Ligands」揭露一種含N^C^N-配位三牙配基的銥金屬錯合物,可做為有機發光二極體(OLED)中的磷光材料。其中所揭露的「Ir(dpyx)(dppy)」及「Ir(dpyx)(F4dppy)」分別為包含雙(三牙配基)的銥金屬錯合物。然而,「Ir(dpyx)(dppy)」及「Ir(dpyx)(F4dppy)」的產率較低(分別為37%及21%),從而增加合成的成本,不利於實際用於有機發光二極體的產業。
由上述可知,若能開發出一種合成產率高、合成成本較低的磷光材料,對有機發光二極體產業的發展必定大有俾益。
因此,本發明之目的,即在提供一合成產率高的含雙(三牙配基)的銥金屬錯合物。
於是本發明含雙(三牙配基)的銥金屬錯合物,是由式(I)所示:
R1表示、或;
R3至R8、R21至R23、R31至R35及R41至R45各自表示H、F、烷基、全氟烷基、烷氧基、芳香基、二甲胺基、二苯胺基或咔唑基;R9至R10各自表示H、F、烷基或烷氧基;X1表示氮或C-X11,X11表示全氟烷基;X2表示氮或CH;X3表示氮或C-X31,X31表示H、F、CN、烷基、全氟烷基、烷氧基或芳香基。
本發明之功效在於:該含雙(三牙配基)的銥金屬錯合物的合成產率較高,從而有利於實際應用至有機發光二極體的產業上。
以下將就本發明內容進行詳細說明:
於本發明中,該烷基例如為C1至C6的烷基。該全氟烷基例如為C1至C6的全氟烷基。該烷氧基例如為C1至C6的烷氧基。該芳香基例如為C6至C10的芳香基,具體例子為苯基或萘基等。
較佳地,X1表示C-X11,X11表示全氟烷基。更佳地,該X11表示CF3。
較佳地,X2表示CH。
較佳地,X3表示C-X31,X31表示H、F、CN、烷基、全氟烷基、烷氧基或芳香基。更佳地,該X31表示H或烷基。於本發明之一具體例中,該X31表示H,且R9及R10分別表示F。於本發明之另一具體例中,該X31表示烷基,且R9及R10分別表示H。
較佳地,R1表示或。更佳地,R21、R22、R23、R31、R32、R33、R34及R35表示氫或烷基。
較佳地,式(I)表示以下的化合物:
更佳地,式(I)表示以下的化合物:
本發明含雙(三牙配基)的銥金屬錯合物可依據各個配基的變化選用適當的反應物及反應條件進行製備,且反應製備方式可依據本領域所熟知的技術進行變化。該含雙(三牙配基)的銥金屬錯合物的製備方式的一具體例包
含以下步驟:將一包含一式(II)所示的化合物及一式(III)所示的銥金屬二聚物的第一混合物加熱進行反應,以製得該含雙(三牙配基)的銥金屬錯合物。
該式(II)所示的化合物,其中,R3至R8及X1至X2的定義是如上所述。
該式(III)所示的銥金屬二聚物,其中,R1、R9、R10及X3的定義是如上所述。該式(III)所示的銥金屬二聚物是由一包含一式(IV)所示的化合物及一銥源的第二混合物加熱進行反應所製得。該式(IV)所示的化
合物,其中,R1、R9、R10及X3的定義是如上所述。該銥源例如但不限於:IrCl3.3H2O、IrCl3(tht)3或[It(COD)Cl]2等,其中,「tht」代表四氫噻吩(tetrahydrothiophene);「COD」代表環辛二烯(cyclooctadiene)。
該第一混合物還包含一觸媒及一第一溶劑。該式(II)中的五元環結構能使式(II)具有較大反應活性,從而在觸媒的選擇上較無限制,可使用較便宜的觸媒,該觸媒
例如但不限於:碳酸鈉、醋酸鈉、醋酸鉀、碳酸氫鈉或碳酸鉀等。該第一溶劑例如但不限於:十氫化萘、三甲苯、二甲苯或二甲基亞碸等。
該第二混合物還包含一第二溶劑。該第二溶劑例如但不限於:乙二醇單乙醚、乙二醇單甲醚、二乙二醇單乙醚或二乙二醇單甲醚等。
本發明含雙(三牙配基)的銥金屬錯合物透過該兩個三牙配基的互相配合,使得該含雙(三牙配基)的銥金屬錯合物經光或電激發後可放射出可見光區域的磷光,能應用做為有機發光二極體的發光層中的客發光體。
該含雙(三牙配基)的銥金屬錯合物透過該兩個三牙配基的互相配合,能使得該含雙(三牙配基)的銥金屬錯合物經光或電激發後可放射出可見光區域的不同發光顏色的磷光。
本發明將就以下實施例來作進一步說明,但應瞭解的是,該實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。
<實施例>
[合成例1]2-[3-(三氟甲基)-1H-5-吡唑基]-6-[4-(三氟甲基)苯基]-吡啶
{2-[3-(trifluoromethyl)-1H-pyrazol-5-yl]-6-[4-(trifluoromethyl)phenyl]-pyridine,以下簡稱L1}
(1).1-(6-溴-2-吡啶基)乙酮[1-(6-bromopyridin-2-yl)ethanone,以下簡稱L1-1]的合成
將10.0克(42.2mmol)2,6-二溴吡啶(2,6-dibromopyridine)置於反應瓶內,快速抽換氮氣三次後,於反應瓶中加入150毫升無水乙醚(anhydrous diethylether),再於-78℃緩緩加入17.7毫升(44.3mmol)正丁基鋰(2.5M溶於正己烷),此時反應瓶中的溶液由透明無色轉成黃褐色,並將反應維持在-78℃且持續攪拌30分鐘後,冰浴下緩慢滴入4.7毫升(50.7mmol)N,N-二甲基乙醯胺(N,N-dimethylacetamide),並維持在-78℃反應3小時,隨後將溫度慢慢回到20℃,此時反應瓶中的溶液產生灰白色混濁,接著緩慢加入去離子水終止反應後,抽乾溶劑,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉(Na2SO4)除水,所得到的粗產物先以二氧化矽(SiO2)管柱層析分離(沖提液為乙酸乙酯:正己烷=1:20),再用二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:20)於20℃下再結晶,得到6.80克白色粉末固體L1-1,產率81%。
L1-1的光譜分析:1H NMR(400MHz,CDCl3):δ 7.97(dd,J=7.0,1.6Hz,1H),7.68(t,J=7.8Hz,1H),7.64(dd,J=8.0,1.2Hz,1H),2.69(s,3H)。該L1-1的結構
為:
(2).4,4,5,5-四甲基-2-[4-(三氟甲基)苯基]-1,3,2-硼戊烷{4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane,以下簡稱L1-2}的合成
將4.8克(21.3mmol)4-溴三氟甲苯(4-bromobenzotrifluoride)置於反應瓶內,快速抽換氮氣三次後,於反應瓶中加入50毫升無水乙醚,再於-78℃緩緩加入10毫升(25.6mmol)正丁基鋰(2.5M溶於正己烷),此時反應瓶中的溶液由透明無色轉成草綠混濁,並將反應維持在-78℃且持續攪拌60分鐘後,於-78℃下緩慢滴入(5.2毫升(25.6mmol)2-異丙基-4,4,5,5-四甲基-1,3,2-硼戊烷(2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane),隨後將溫度慢慢回到20℃並反應12小時,反應瓶中的溶液會由草綠色混濁轉成乳白混濁,之後緩慢加入去離子水終止反應,抽乾溶劑,用乙酸乙酯及飽和食鹽水分別清洗數次,收集有機層並用硫酸鈉除水,所得到的粗產物以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)於20℃下再結晶,得到4.27克白色粉末固體L1-2,產率73%。
L1-2的光譜分析:1H NMR(400MHz,CDCl3):δ 7.88(d,J=8.0,2H),7.59(d,J=8.0Hz,2H),1.33(s,12H);19F NMR(376MHz,CDCl3,298K):δ -63.06(s)。該
L1-2的結構為:
(3).1-[6-(4-(三氟甲基)苯基)-2-吡啶基]乙酮
{1-[6-(4-(trifluoromethyl)phenyl)pyridin-2-yl]ethanone,以下簡稱L1-3}的合成
將900毫克(4.5mmol)的L1-1、1.36克(5mmol)L1-2、11毫升(22.5mmol)濃度為2N的Na2CO3溶液,及260毫克(0.22mmol)四(三苯基膦)鈀[Pd(PPh3)4]置於反應瓶中,再加入27毫升甲苯(toluene)及3毫升甲醇,加熱迴流反應24小時後,將溫度慢慢回到20℃,抽乾溶劑,用乙酸乙酯及飽和食鹽水分別清洗數次,收集有機層並用硫酸鈉除水,所得到的粗產物先以二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:6),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)於20℃下再結晶,得到891毫克白色粉末固體L1-3,產率75%。
L1-3的光譜分析:1H NMR(400MHz,CDCl3):δ 8.02(d,J=6.4,2H),7.95(d,J=7.6Hz,1H),7.93~7.91(m,2H),7.75(d,J=8.0,2H),2.81(s,3H);19F NMR(376MHz,CDCl3,298K):δ -62.59(s,3F)。該L1-3的結構為:
(4).2-[3-(三氟甲基)-1H-5-吡唑基]-6-[4-(三氟甲基)苯基]-吡啶(L1)的合成
在一反應瓶中將334.8毫克(4.90mmol)的乙醇鈉溶在50毫升無水四氫呋喃中,冰浴下持續攪拌10分鐘後,冰浴下緩慢加入870毫克(3.28mmol)的L1-3並攪拌1小時,再將0.62毫升(4.90mmol)三氟乙酸乙酯(ethyl
trifluoroacetate)加至反應瓶中後將溫度回到室溫(20℃),加熱迴流反應12小時。之後,將溫度降回室溫後(20℃),移除溶劑,加入去離子水,再以濃度為2N的鹽酸調整到弱酸性(pH=5至6),再用乙酸乙酯清洗數次,收集有機層並用硫酸鈉除水,移除溶劑,得到褐色油狀的1,3-二酮(1,3-dione)衍生物中間體。
接著,將1,3-二酮衍生物中間體置於單頸瓶中,以50毫升乙醇溶解,並加入1.6毫升(32.8mmol)水合肼(hydrazine monohydrate)後,加熱迴流反應1天。反應結束後移除溶劑,再用乙酸乙酯及飽和食鹽水分別清洗數次,收集有機層並用硫酸鈉除水後,再以二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:3)管柱層析分離,所得到的產物再用二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)於20℃下再結晶,得到0.84克的白色固體L1,產率70%。
L1的光譜分析:1H NMR(400MHz,CDCl3):δ 11.42(br,1H),8.12(d,J=8.0Hz,2H),7.90(t,J=7.8Hz,1H),7.75(d,J=8.0Hz,3H),7.61(d,J=8.0Hz,1H),6.99(s,1H);19F NMR(376MHz,CDCl3,298 K):δ -62.35(s,3F),
-62.69(s,3F)。該L1的結構為:
[合成例2]2-[3-(第三丁基)-1H-5-吡唑基]-6-[4-(三氟甲基)苯基]-吡啶{2-[3-(tert-butyl)-1H-pyrazol-5-yl]-6-[4-(trifluoromethyl)p
henyl]-pyridine,以下簡稱L2}
(1)1-[6-(4-(第三丁基)苯基)-2-吡啶基]乙酮{1-[6-(4-(tert-butyl)phenyl)pyridin-2-yl]ethanone,以下簡稱L2-1}的合成
L2-1的反應步驟是與L1-3的反應步驟相同,差別在於使用1.29克(4.74mmol)的L1-2,所得到的粗產物先以二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:5),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)於20℃下再結晶,得到1113毫克淡黃色液體L2-1,產率97.8%。
L2-1的光譜分析:1H NMR(400MHz,CDCl3):δ 8.02(d,J HH =8.4Hz,2H),7.94~7.83(m,3H),7.52(d,J HH =8.4Hz,2H),2.8(s,3H),1.36(s,9H)。該L2-1的結構為:
(2).2-[3-(第三丁基)-1H-5-吡唑基]-6-[4-(三氟甲基)苯基]-吡啶{2-[3-(tert-butyl)-1H-pyrazol-5-yl]-6-[4-(trifluoromethyl)phenyl]-pyridine,以下簡稱L2}的合成
L2的反應步驟是與L1的反應步驟相同,差別在於用253毫克(1mmol)的L2-1取代L1-3,所得到的粗產物先以二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:5),得到1877毫克白色固體L2,產率56.1%。
L2的光譜數據:1H NMR(400MHz,CDCl3):δ
7.95(dd,J HH =8.4,2.0Hz,2H),7.83(t,J HH =8.0Hz 1H),7.70(d,J HH =8.0Hz 1H),7.54(d,J HH =2.0Hz,1H),7.53~7.51(m,2H),6.96(s,1H),1.37(s,9H);19F NMR(376MHz,CDCl3):δ -62.37(s,3F)。該L2的結構為:
[合成例3]1,3-二(2-吡啶基)-4,6-二氟苯[1,3-di(2-pyridyl)-4,6-difluorobenzene,以下簡稱L3]
(1).1,5-二溴-2,4-二氟苯(1,5-dibromo-2,4-difluorobenzene,以下簡稱L3-1)的合成
將3克(15.5mmol)2,4-二氟溴苯(2,4-difluorobromobenzene)及260毫克鐵屑(iron filings)置於雙頸瓶中,再於雙頸瓶中加入15毫升二氯甲烷,並在等壓加料管內裝入1毫升(18.7mmol)溴(bromine)及15毫升二氯甲烷的混合溶液,於冰浴下將該混合溶液緩慢滴入該雙頸瓶中,加熱迴流反應3小時,此時會有棕色氣體產生,將溫度降回20℃後加入50毫升的10%焦亞硫酸鈉(Na2S2O5)水溶液攪拌一小時以終止反應,以去離子水清洗數次,收集有機層並用硫酸鈉除水,移除溶劑,再以二氧化矽管柱層析分離(沖提液為正己烷),得到3.5克白色晶體(L3-1),產率83%。
L3-1的光譜數據:1H NMR(400MHz,CDCl3):δ 7.74(t,J=7.6Hz,1H),6.96(t,J=8.0Hz,1H);19F
NMR(376MHz,CDCl3,298 K):δ -103.8(dd,J=7.5Hz,J=
7.5Hz)。該L3-1的結構為:
(2).2-(三丁基锡)吡啶[2-(tributylstannyl)pyridine,以下簡稱L3-2]的合成
將3.3克(21.0mmol)2-溴吡啶(2-bromopyridine)置於反應瓶內,快速抽換氮氣三次,再於反應瓶中加入30毫升無水四氫呋喃,在-78℃下緩緩加入9毫升(23.0mmol)正丁基鋰(2.5M溶於正己烷)後,攪拌60分鐘,此時溶液由深褐色澄清轉成草黃色混濁,接著於-78℃下緩慢滴入6.3毫升(23.0mmol)三丁基氯化錫(tributyltin chloride),反應3小時,隨後將溫度慢慢回到20℃,再攪拌30分鐘,此時溶液變為黃色澄清,之後緩慢加入飽和氯化銨(NH4Cl)水溶液終止反應,抽乾溶劑,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉除水,得到7.53克深褐色液體L3-2,產率98%。
L3-2的光譜數據:1H NMR(400MHz,CDCl3):δ 8.66(d,J=1.2Hz,1H),7.49(m,1H),7.40(d,J=1.2Hz,1H),7.09~7.13(m,1H),1.57(m,6H),1.30~1.35(m,6H),1.10~1.14(m,6H),0.88(t,J=7.2Hz,9H)。該L3-2的結構
為。
(3).1,3-二(2-吡啶基)-4,6-二氟苯(L3)的合成
將0.12克(0.17mmol)雙三苯基磷二氯化鈀[Pd(PPh3)2Cl2]及1.5克(5.5mmol)的L3-1置於反應瓶內,並
於反應瓶中加入1.4克(33.1mmol)氯化鋰(lithium chloride)、6克(16.6mmol)的L3-2及40毫升的無水甲苯,加熱迴流反應三天,隨後將溫度慢慢回到20℃後,以矽藻土(celite)過濾掉反應副產物,收集濾液,抽乾濾液中的溶劑,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉除水,所得到的粗產物先以二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:3),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)於20℃下再結晶,得到780毫克透明晶體L3,產率53%。
L3的光譜數據:1H NMR(400MHz,d 6 -acetone):δ 8.84(t,J=6.8Hz,1H),8.74(d,J=4.8Hz,2H),7.94~7.87(m,4H),7.41~7.38(m,2H),7.29(t,J=9.4Hz,1H);19F NMR(376MHz,d 6 -acetone,decouple H,298
K):δ -112.95。該L3的結構為:。
[合成例4]2,2'-(4,6-二氟-1,3-伸苯基)雙[4-(第三丁基)吡啶]{2,2'-(4,6-difluoro-1,3-phenylene)bis[4-(tert-butyl)pyridine],以下簡稱L4}
(1).4-(第三丁基)吡啶N-氧化物[4-(tert-butyl)pyridine N-oxide,以下簡稱L4-1]的合成
將13.5克(99.8mmol)4-(第三丁基)吡啶[4-(tert-butyl)pyridine]溶於70毫升(1.29mmol)冰醋酸,再緩慢加入30毫升(0.30mol)的30%雙氧水(H2O2),加熱至80
℃,反應24小時後,將溫度慢慢回到20℃,利用真空移除溶劑,以氫氧化鈉水溶液[NaOH(aq)]中和至微鹼性(pH=8),用CH2Cl2及去離子水分別水洗數次,收集有機層並用硫酸鈉除水,移除溶劑,再利用真空乾燥,得到13克淡黃色固體L4-1,產率87%。
該L4-1的結構為:
(2).4-(第三丁基)-2-氯吡啶[4-(tert-butyl)-2-chloropyridine,以下簡稱L4-2]的合成
將5克(33.07mmol)的L4-1置於雙頸瓶中,在冰浴下緩慢加入25毫升三氯氧磷(POCl3),加熱至迴流,反應24小時後,將溫度慢慢回到室溫(20℃),利用真空移除溶劑,並以飽和碳酸鈉水溶液中和,再用乙酸乙酯萃取,收集有機層並用硫酸鈉除水,所得到的粗產物用二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:6),得到4克透明液體L4-2,產率72%。
L4-2的光譜數據:1H-NMR(400MHz,CDCl3):δ 8.27(d,J=5.3Hz,1H),7.28(s,1H),7.19(dd,J=5.2Hz,
1.6Hz,1H),1.29(s,9H)。該L4-2的結構為:。
(3).4-(第三丁基)-2-溴吡啶[4-(tert-butyl)-2-bromopyridine,以下簡稱L4-3]的合成
將3克(17.6mmol)的L4-2及7毫升(53.05mmol)
三甲基溴(trimethylsilyl bromide)置於反應瓶中,於反應瓶中加入50毫升丙腈(propionitrile),加熱至迴流,反應24小時後,靜置溫度回到室溫(20?℃),再加入7毫升(53.05mmol)三甲基溴,加熱至迴流,反應24小時後,將溫度慢慢回到室溫(20℃),利用真空移除反應溶劑,用飽和碳酸鈉水溶液中和,再用乙酸乙酯萃取,收集有機層並用硫酸鈉除水,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉除水,所得到的粗產物用二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:6),得到3克黃色油狀液體L4-3,產率80%。
L4-3的光譜數據:1H NMR(400MHz,CDCl3):δ 8.22(d,J=5.2Hz,1H),7.41(s,1H),7.20(dd,J=5.2Hz,
1.6Hz,1H),1.26(s,9H)。該L4-3的結構為:。
(4).2,2'-(4,6-二氟-1,3-伸苯基)雙[4-(第三丁基)吡啶]2,2'-(4,6-二氟-1,3-亞苯基)雙(4,4,5,5-四甲基-1,3,2-二氧硼戊環)[2,2'-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane),以下簡稱L4-4]的合成
將300毫克(1.1mmol)1,3-二溴-4,6-二氟苯(1,3-dibromo-4,6-difluorobenzene)、620毫克(2.4mmol)雙聯頻哪醇硼酸酯[bis(pinacolato)diboron]、54毫克(0.07mmol)[1,1'-雙(二苯基膦)二茂鐵]二氯化鈀{[1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(
II),簡稱Pd(dppf)Cl2},及545毫克(5.6mmol)醋酸鉀(potassium acetate)置於反應瓶內,抽真空及灌氮氣重複三次,再加入5毫升無水二甲基亞碸(dimethyl sulfoxide,DMSO),加熱至85℃,反應18小時後,將溫度慢慢回到室溫(20℃),抽乾溶劑,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉除水,所得到的粗產物用二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:4),接著以正己烷於高溫下溶解後放置在冰箱整晚(12小時),得到496毫克白色固體L4-4,產率45%。
L4-4的光譜數據:1H NMR(400MHz,CDCl3):δ 8.11(t,J=7.5Hz,1H),6.71(t,J=9.2Hz,1H),1.33(s,24 H);19F NMR(376MHz,CDCl3,298 K):δ -94.18(t,J=
11.2Hz)。該L4-4的結構為:。
(5).2,2'-(4,6-二氟-1,3-伸苯基)雙[4-(第三丁基)吡啶](L4)的合成
將0.32克(0.27mmol)雙(三苯基磷)二氯化鈀[Pd(PPh3)2Cl2]、1克(2.7mmol)的L4-4、1.29克(6mmol)的L4-3,及15毫升濃度為2N的碳酸鈉置於反應瓶內,再加入15毫升乙二醇二甲醚(dimethoxyethane),加熱至迴流,反應兩天後,將溫度慢慢回到室溫(20℃),抽乾溶劑,用乙酸乙酯及飽和食鹽水分別水洗數次,收集有機層並用硫酸鈉除水,所得的粗產物用二氧化矽管柱層析分離(沖提液為
乙酸乙酯:正己烷=1:3.5),得到520毫克無色液體L-4,產率50%。
L-4的光譜數據:1H NMR(400MHz,d 6 -acetone):δ 8.74(t,J=9.2Hz,1H),8.64(d,J=5.2Hz,2H),7.88(s,2 H),7.43(dd,J=5.2,2.0Hz,2H),7.30(t,J=11.2Hz,1H),1.38(s,18H);19F NMR(376MHz,d 6 -acetone,298 K):δ -113.42(t,J=10.2Hz)。該L-4的結構為
[合成例5]2,2'-[5-(第三丁基)-1,3-伸苯基]二吡啶{2,2'-[5-(tert-butyl)-1,3-phenylene]dipyridine,以下簡稱L5}
(1).2,2'-[5-(第三丁基)-1,3-伸苯基]雙(4,4,5,5-四甲基-1,3,2-二氧硼戊環){2,2'-[5-(tert-butyl)-1,3-phenylene]bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane),以下簡稱L5-1}的合成
將2.9克(10mmol)1,3-二溴-5-第三丁基苯(1,3-dibromo-5-tert-butylbenzene)、5克(20mmol)雙聯頻哪醇硼酸酯bis(pinacolato)diboron、4.9克(50mmol)醋酸鉀、0.5克(0.7mmol)[1,1'-雙(二苯基膦)二茂鐵]二氯化鈀,及100毫升1,4-二噁烷(1,4-dioxane)置於反應瓶內,在氮氣保護下於100℃反應12小時後冷卻,接著將反應瓶中的混合物與水混合,並用乙酸乙酯萃取,收集有機層並用飽和食鹽水洗後再用無水硫酸鈉乾燥,減壓以去除溶劑,所得到的粗
產物用二氧化矽管柱層析分離(沖提液為正己烷),得到2.4克白色固體L5-1,產率63%。
L5-1的光譜數據:1H NMR(CDCl3,400MHz):δ 8.09(s,1H),7.91(s,2H),1.34(s,9H),1.32(s,24H)。該
L5-1的結構為:。
(2).2,2'-[5-(第三丁基)-1,3-伸苯基]二吡啶(L5)的合成
將3.2克(20mmol)2-溴吡啶(2-bromopyridine)、3.9克(10mmol)的L5-1、3克(30mmol)碳酸鈉、0.5克(0.4mmol)四(三苯基膦)鈀,及15毫升乙二醇二甲醚及15毫升水的混合液置於反應瓶內,在氮氣保護下於100℃反應24小時後冷卻,接著將反應瓶中的混合物與水混合,並用乙酸乙酯萃取,收集有機層並用飽和食鹽水洗後再用無水硫酸鈉乾燥,減壓以去除溶劑,所得到的粗產物用二氧化矽管柱層析分離(沖提液為正己烷:乙酸乙酯=1:5),得到2.4克白色固體L5,產率63%。
L5的光譜數據:1H NMR(CDCl3,400MHz):δ 8.70(d,J=5.6Hz,2H),8.35(s,1H),8.12(s,2H),7.81(d,J=6.0Hz,2H),7.73(t,J=7.6Hz,2H),7.19~7.22(m,2H),
1.44(s,9H)。該L5的結構為:。
[合成例6]{1,1'-[5-(tert-butyl)-1,3-phenylene]diisoquinoline,以下簡稱L6}
合成例6的反應步驟是與合成例5的反應步驟相同,差別在於用3.3克(20mmol)1-氯異喹啉(1-chloroisoquinoline)取代2-溴吡啶,所得到的粗產物用二氧化矽管柱層析分離(沖提液為乙酸乙酯:正己烷=1:4),得到4克白色固體L6,產率52%。
L6的光譜數據:1H NMR(CDCl3,400MHz):δ 8.60(d,J=6.0Hz,2H),8.16(d,J=9.2Hz,2H),7.85(s,2H),7.82(d,J=8.0Hz,2H),7.79(t,J=1.6Hz,1H),7.60~7.64(m,4H),7.49(t,J=7.2Hz,2H),1.42(s,9H)。
該L6的結構為:。
[合成例7]銥金屬二聚物
將200毫克(0.57mmol)IrCl‧3H2O及153毫克(0.57mmol)合成例3置於反應瓶中,於反應瓶中加入14毫升乙二醇單乙醚(2-ethoxyethanol)及6毫升的水,加熱至迴流,反應溶液的顏色會由黑色混濁變至黃色混濁,反應24小時後,靜置使反應溶液的溫度回到室溫(20℃),過濾得到固體,再依序用乙醚及乙醇清洗固體後,乾燥後得到236毫克的黃色固體(合成例7銥金屬二聚物),產率77%。
合成例7銥金屬二聚物的光譜數據:1H
NMR(400MHz,d 6 -DMSO):δ 9.07(d,J=5.6Hz,4H),8.14(d,J=3.7Hz,8H),7.65~7.61(m,4H),7.25(t,J=11.6Hz,2H);19F NMR(376MHz,d 6 -DMSO,298 K):δ -106.94(t,J=12.1Hz)。該合成例7銥金屬二聚物的結構為:
[合成例8]銥金屬二聚物
合成例8的反應步驟是與合成例7的反應步驟相同,差別在於用217毫克(0.57mmol)的合成例4取代合成例3,所得到的產物依序用乙醚及乙醇清洗,得到275毫克的黃色固體(合成例8銥金屬二聚物),產率75%
合成例8銥金屬二聚物的光譜數據:1H NMR(400MHz,d 6 -DMSO):δ 8.91(d,J=6.2Hz,4H),8.03(s,4H),7.70(d,J=6.2Hz,4H),7.24(t,J=10.5Hz,2H),1.38(s,36H);19F NMR(376MHz,d 6 -DMSO,298 K):δ -107.51(t,J=11.9Hz)。該合成例8銥金屬二聚物的結構
為:。
[合成例9]銥金屬二聚物
合成例9的反應步驟是與合成例7的反應步驟相同,差別在於用164毫克(0.57mmol)的合成例5取代合成例3,所得到的產物依序用乙醚及乙醇清洗,得到227毫克的棕黃色固體(合成例9銥金屬二聚物),產率72.5%
合成例9銥金屬二聚物的光譜數據:1H NMR(400MHz,d 6 -DMSO):δ 9.01(d,J=4.8Hz,4H),8.32(t,J=7.2Hz,4H),7.99(s,4H),7.92(t,J=7.6Hz,4H),7.35(t,J=7.2Hz,4H),1.44(s,18H)。該合成例9銥金屬
二聚物的結構為:
[合成例10]銥金屬二聚物
合成例10的反應步驟是與合成例7的反應步驟相同,差別在於用221毫克(0.57mmol)的合成例6取代合成例3,所得到的產物依序用乙醚及乙醇清洗,得到286毫克的紅色固體(合成例10銥金屬二聚物),產率77%
合成例10銥金屬二聚物的光譜數據:1H NMR(400MHz,d 6 -DMSO):δ 9.17(d,J=6.4Hz,2H),9.09(t,J=7.6Hz,4H),8.93(s,2H),8.56(d,J=6.4Hz,4H),
8.22(d,J=8.0Hz,4H),8.05(d,J=6.4Hz,2H),7.96~8.02(m,6H),7.87~7.94(m,4H),1.58(s,9H),1.57(s,9H)。該
合成例10銥金屬二聚物的結構為:
[實施例1]含雙(三牙配基)的銥金屬錯合物
將50毫克(0.046mmol)的合成例7及42毫克(0.11mmol的合成例1置於反應瓶中,於反應瓶中加入82毫克(1.0mmol)醋酸鈉(sodium acetate)及20毫升十氫化萘(decalin),在氮氣保護下加熱至迴流,反應24小時後,靜置回至室溫,以真空抽乾溶劑,所得到的粗產物以二氧化矽管柱層析分離(沖提液為二氯甲烷:乙酸乙酯=5:1),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1)重結晶,得到54毫克的亮黃色固體(實施例1),產率72%。
實施例1的光譜數據:1H NMR(400MHz,CDCl3):δ 8.10(d,J=4.0Hz,2H),7.96(t,J=8.0Hz,1H),7.81(d,J=8.0Hz,1H),7.76(d,J=8.0Hz,1H),7.62~7.55(m,4H),7.30(d,J=4.0Hz,2H),6.99(d,J=8.0Hz,1H),6.88(s,1H),6.73(t,J=4.0Hz,2H),6.06(s,1H);19F NMR(376MHz,CDCl3,298 K):δ -60.15(s,3F),-62.85(s,3F),
-107.65(d,J=12.4Hz,2F);MS[FAB],m/z 816.1,M+;C32H16F8IrN5.H2O元素分析計算值:C,44.24;H,2.55;N,8.06%;理論值:C,44.55;H,2.58;N,7.99%。該實施例1的結構為:
[實施例2]含雙(三牙配基)的銥金屬錯合物
實施例2的反應步驟是與實施例1的反應步驟相同,差別在於用59毫克(0.046mmol)的合成例8取代合成例7,所得到的粗產物以二氧化矽管柱層析分離(沖提液為二氯甲烷:乙酸乙酯=5:1),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1),得到48毫克的亮黃色固體(實施例2),產率56%。
實施例2的光譜數據:1H NMR(400MHz,CDCl3):δ 8.09(s,2H),7.93(d,J=8.0Hz,1H),7.79(d,J=8.0Hz,1H),7.74(d,J=8.0Hz,1H),7.61(d,J=8.0Hz,1H),7.15(d,J=8.0Hz,2H),7.00(d,J=8.0Hz,1H),6.89(s,1H),6.83(t,J=8.0Hz,1H),6.72~6.70(m,2H),6.12(s,1H),1.24(s,18H);19F NMR(376MHz,CDCl3,298 K):δ -59.98(s,3F),-62.68(s,3F),-108.43(d,J=4.0Hz,2F).MS[FAB],m/z 926,M+;C40H32F81rN5元素分析計算值:C,
51.83;H,3.48;N,7.56%;理論值:C,51.51;H,3.51;N,7.63%。該實施例2的結構為:
[實施例3]含雙(三牙配基)的銥金屬錯合物
實施例3的反應步驟是與實施例1的反應步驟相同,差別在於用51毫克(0.046mmol)的合成例9取代合成例7,所得到的粗產物以氧化鋁(Al2O3)管柱層析分離(沖提液為二氯甲烷:正己烷=1:1),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1),得到52毫克的亮黃色固體(實施例3),產率68%。
實施例3的光譜數據:1H NMR(CDCl3,400MHz):δ 8.10(s,2H),7.97~8.01(m,3H),7.90(d,J=8.0Hz,1H),7.82(d,J=8.0Hz,1H),7.70(d,J=8.4Hz,1H),7.63(t,J=8.4Hz,2H),7.40(d,J=5.6Hz,2H),7.0(d,J=10.0Hz,1H),6.91(s,1H),6.77(t,J=7.2Hz,2H)6.07(s,1H),1.62(s,9H);19F NMR(CDCl3,376MHz):δ -60.67(s,3F),-63.16(s,3F);MS[FAB],m/z 836.1,[M+H]+。該實施例3的結構為:
[實施例4]含雙(三牙配基)的銥金屬錯合物
實施例4的反應步驟是與實施例1的反應步驟相同,差別在於用60毫克(0.046mmol)的合成例10取代合成例7,所得到的粗產物以氧化鋁(Al2O3)管柱層析分離(沖提液為二氯甲烷:正己烷=1:1),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1),得到45毫克的紅色固體(實施例4),產率52%。
實施例4的光譜數據:1H NMR(CDCl3,400MHz):δ 9.23(d,J=8.8Hz,2H),8.91(s,2H),8.06(t,J=8.0Hz,1H),7.94(d,J=8.0Hz,1H),7.90(d,J=8.0Hz,1H),7.84(t,J=8.4Hz,2H),7.80(d,J=68Hz,2H),7.74(d,J=6.8Hz,1H),7.73(t,J=7.6Hz,1H),7.68(d,J=8.0Hz,1H),7.36(d,J=6.4Hz,2H),7.15(d,J=6.4Hz,2H),6.93(d,J=7.6Hz,2H),5.63(s,1H),1.73(s,9H);19F NMR(CDCl3,376MHz):δ -60.73(s,3F),-63.34(s,3F);MS[FAB],m/z 936,[M+H]+。該實施例4的結構為:
[實施例5]含雙(三牙配基)的銥金屬錯合物
實施例5的反應步驟是與實施例1的反應步驟相同,差別在於用55毫克(0.05mmol)的合成例9取代合成例7,以及用35毫克(0.1mmol)的合成例2取代合成例1,所得到的粗產物以氧化鋁(Al2O3)管柱層析分離(沖提液為二氯甲烷),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1),得到46毫克的亮黃色固體(實施例5),產率56%。
實施例5的光譜數據:1H NMR(400MHz,CDCl3):δ 7.92(d,J=7.6Hz,2H),7.87(d,J=8.4Hz,2H),7.78(d,J=8.0Hz,1H),7.74(d,J=7.6Hz,1H),7.54(t,J=8.4Hz,2H),7.44(d,J=8.4Hz,1H),7.41(t,J=7.6Hz,1H),7.34(d,J=5.6Hz,2H),6.95(s,1H),6.77(d,J=8.4Hz,1H),6.70(t,J=5.6Hz,2H),5.70(s,1H),1.24(s,9H),0.85(s,9H);19F NMR(376MHz,CDCl3):δ -59.88(s,3F);MS[FAB],m/z 824,[M+H]+。該實施例5的結構為:
[實施例6]含雙(三牙配基)的銥金屬錯合物
實施例6的反應步驟是與實施例1的反應步驟相同,差別在於用65毫克(0.05mmol)的合成例10取代合成例7,以及用35毫克(0.1mmol)的合成例2取代合成例,所得到的粗產物以氧化鋁(Al2O3)管柱層析分離(沖提液為二氯甲烷),再以二氯甲烷及正己烷的混合液(CH2Cl2:hexane=1:1),得到58毫克的紅色固體(實施例6),產率63%。
實施例6的光譜數據:1H NMR(400MHz,CDCl3):δ 9.13(d,J=8.8Hz,2H),8.79(s,2H),7.91(t,J=7.6Hz,1H),7.73~7.77(m,4H),7.71(d,J=7.2Hz,2H),7.64(t,J=7.6Hz,2H),7.42(d,J=8.0Hz,1H),7.36(d,J=6.4Hz,2H),7.04(d,J=6.4Hz,2H),6.89(s,1H),6.68(d,J=8.0Hz,1H),5.20(s,1H),1.68(s,9H),0.74(s,9H);19F NMR(376MHz,CDCl3):δ -60.42(s,3F);MS[FAB],m/z 925,[M+H]+。該實施例6的結構為:
<應用例>
[應用例1至4]有機發光二極體(OLED)
(1).以電子級清潔劑、去離子水、丙酮及甲醇依序震盪清洗一氧化銦錫(ITO)玻璃基板(即表面鍍有ITO的玻璃基板,在元件中作為陽極,片電阻值10ohm/square)。震盪清洗完後,使用乾燥氮氣吹乾ITO玻璃基板,並以紫外光臭氧機(UV-ozone cleaner)照射ITO玻璃基板,增加ITO的功函數及ITO玻璃基板的清潔度。
(2).ITO玻璃基板清洗後,使用真空熱蒸鍍機,以真空熱蒸鍍(thermal evaporation)的方式在壓力小於10-6torr及沉積速率為0.2nm/s下於該ITO玻璃基板的ITO上依序蒸鍍一電洞傳輸層、一發光層(包含客發光體及主發光體)、一電子傳輸層、一電子注入層[材料為氟化鋰(LiF))及一陰極[材料為鋁(Al)],即製得應用例1至4的有機發光二極體。其中,應用例1至4有機發光二極體中的電洞傳輸層、發光層(包含客發光體及主發光體)、電子傳輸層的材料及厚度是如表2所示。
<評價項目>
1.吸收波長:
將實施例1至6的含雙(三牙配基)的銥金屬錯合物分別溶解於二氯甲烷中(濃度:10-5M),以紫外光/可見光光譜儀(廠商:Hitachi Spectrophotometer,型號:U-3900)測量實施例1至6在溶液狀態時的吸收光譜(單位:nm)及莫耳消光係數(molar extinction coefficient,以ε表示,單位:M-1cm-1),測量範圍250nm至700nm。
2.放光波長:
將實施例1至6的含雙(三牙配基)的銥金屬錯合物分別溶解於二氯甲烷中(濃度為10-5M),以螢光光譜儀(廠商:Edinburgh Instrument,型號:FLS920)測量每一實施例於溶液狀態時的螢光光譜(單位:nm),測量範圍400nm至800nm。
3.量子效率(Φsol):
將實施例1至6的含雙(三牙配基)的銥金屬錯合物分別溶解於二氯甲烷中(濃度為10-5M),使用螢光光譜儀(廠商:Edinburgh Instrument,型號:FLS920)於室溫(20℃)下以激發波長為350nm測量每一實施例的量子效率(Φsol)。其中,測量實施例1至3及5時的標準物為:在乙醇中量子效率為0.764的奎寧。測量實施例4及6時的標準物為:在乙醇中量子效率為0.435的4-(二氰基伸甲基)-2-甲基-6-(4-二甲基胺基苯乙烯基)-4H-吡喃[4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran]。
4.發光壽命()、非輻射放光速率常數(knr)
及輻射放光速率常數(kr):
將實施例1至6的含雙(三牙配基)的銥金屬錯合物以螢光光譜儀(廠商:Edinburgh Instrument,型號:FLS920)的光子計數系統並利用氫或氮燈作為激發源,測量實施例1至6的發光壽命(emission lifetime,)。並利用以下公式計算得到實施例1至6的非輻射放光速率常數(nonradiative decay rate constant,knr)及輻射放光速率常數(radiative decay rate constant,kr)。
4.有機發光二極體的性質(外部量子效率、發光效率、發光功率、色度及最大亮度):
在手套箱中量測應用例1至4的有機發光二極體的性質。先以一電壓電流計提供一驅動電壓驅動有機發光二極體,同時量測最大電流密度。再利用光偵測二極體(Photodiodes,廠牌:UDT,型號:PIN-10DP)量測有機發光二極體的放光強度。知道電流-電壓-輝度(I-V-L)的關係,可經由公式推算出有機發光二極體的外部量子效率(external quantum efficiency),再利用光譜儀(廠牌:OTO,型號:SD1200)量測有機發光二極體的電激發光頻譜(Electroluminescence,EL)。並經由公式轉換及計算後,得到色度、最大亮度、發光效率及發光功率。
由表1可知,實施例1至6含雙(三牙配基)的銥金屬錯合物的產率為52%至72%,具有較高的產率。
綜上所述,本發明含雙(三牙配基)的銥金屬錯合物的合成產率高,從而能降低合成的成本,有利於實際應用至於有機發光二極體的產業上,故確實能達成本發明之目的。
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。
Claims (10)
- 一種含雙(三牙配基)的銥金屬錯合物,是由式(I)所示:
- 如請求項1所述的含雙(三牙配基)的銥金屬錯合物,其中,X1表示C-X11,X11表示全氟烷基。
- 如請求項1或2所述的含雙(三牙配基)的銥金屬錯合 物,其中,X2表示CH。
- 如請求項3所述的含雙(三牙配基)的銥金屬錯合物,其中,R3、R4、R5、R6及R7表示氫,以及R8表示烷基或全氟烷基。
- 如請求項1所述的含雙(三牙配基)的銥金屬錯合物,其中,X3表示C-X31,X31表示H、F、CN、烷基、全氟烷基、烷氧基或芳香基。
- 如請求項5所述的含雙(三牙配基)的銥金屬錯合物,其中,X31表示H,且R9及R10分別表示F。
- 如請求項5所述的含雙(三牙配基)的銥金屬錯合物,其中,X31表示烷基,且R9及R10分別表示H。
- 如請求項1、5、6及7中任一項所述的含雙(三牙配基)的銥金屬錯合物,其中,R1表示或。
- 如請求項8所述的含雙(三牙配基)的銥金屬錯合物,其中,R21、R22、R31、R32、R33及R34表示氫或烷基,R23及R35表示氫或C1至C6烷基。
- 如請求項1所述的含雙(三牙配基)的銥金屬錯合物,是 選自於、、
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW103144964A TWI546309B (zh) | 2014-12-23 | 2014-12-23 | 含雙(三牙配基)的銥金屬錯合物 |
CN201410833902.3A CN105801627B (zh) | 2014-12-23 | 2014-12-29 | 含双三齿配体的铱金属配合物 |
US14/660,156 US9219237B1 (en) | 2014-12-23 | 2015-03-17 | Heteroleptic Ir(III) phosphors with bis-tridentate chelating architecture for high efficiency OLEDs |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW103144964A TWI546309B (zh) | 2014-12-23 | 2014-12-23 | 含雙(三牙配基)的銥金屬錯合物 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201623320A TW201623320A (zh) | 2016-07-01 |
TWI546309B true TWI546309B (zh) | 2016-08-21 |
Family
ID=54848038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103144964A TWI546309B (zh) | 2014-12-23 | 2014-12-23 | 含雙(三牙配基)的銥金屬錯合物 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9219237B1 (zh) |
CN (1) | CN105801627B (zh) |
TW (1) | TWI546309B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106663740B (zh) * | 2014-07-24 | 2018-08-14 | 环球展览公司 | 具有增强层的oled装置 |
US10396298B2 (en) * | 2017-01-25 | 2019-08-27 | National Tsing Hua University | Iridium complex and organic light-emitting diode using the same |
KR20200138533A (ko) * | 2019-05-30 | 2020-12-10 | 삼성디스플레이 주식회사 | 유기금속 화합물 및 이를 포함한 유기 발광 소자 |
KR20210066073A (ko) | 2019-11-27 | 2021-06-07 | 삼성디스플레이 주식회사 | 유기금속 화합물 및 이를 포함한 유기 발광 소자 |
KR20210067007A (ko) | 2019-11-28 | 2021-06-08 | 삼성디스플레이 주식회사 | 유기금속 화합물, 이를 포함하는 유기 발광 소자 및 이를 포함하는 장치 |
KR20210072859A (ko) | 2019-12-09 | 2021-06-18 | 삼성디스플레이 주식회사 | 유기 전계 발광 소자 및 유기 전계 발광 소자용 유기 금속 화합물 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201329065A (zh) * | 2012-01-09 | 2013-07-16 | Nat Univ Tsing Hua | 2-苯基-6-唑基吡啶系配基及由其所形成的第八族過渡金屬錯合物 |
US8580961B2 (en) | 2010-12-13 | 2013-11-12 | National Tsing Hua University | 2-phenyl-6-azolylpyridine-based ligand and group VIII transition metal complex |
CN102268250A (zh) * | 2011-05-31 | 2011-12-07 | 江西理工大学 | 新型电中性三齿铱[iii]配合物红光材料及制备方法 |
-
2014
- 2014-12-23 TW TW103144964A patent/TWI546309B/zh not_active IP Right Cessation
- 2014-12-29 CN CN201410833902.3A patent/CN105801627B/zh not_active Expired - Fee Related
-
2015
- 2015-03-17 US US14/660,156 patent/US9219237B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
TW201623320A (zh) | 2016-07-01 |
CN105801627B (zh) | 2018-06-08 |
US9219237B1 (en) | 2015-12-22 |
CN105801627A (zh) | 2016-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI546309B (zh) | 含雙(三牙配基)的銥金屬錯合物 | |
Tang et al. | Novel yellow phosphorescent iridium complexes containing a carbazole–oxadiazole unit used in polymeric light-emitting diodes | |
Zhou et al. | Substituent effect of ancillary ligands on the luminescence of bis [4, 6-(di-fluorophenyl)-pyridinato-N, C 2′] iridium (iii) complexes | |
TWI586672B (zh) | 有機金屬化合物及包含其之有機電激發光裝置 | |
TWI421255B (zh) | 有機金屬化合物及包含其之有機電激發光裝置 | |
TW201204808A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
JP5907069B2 (ja) | 電子輸送材料およびこれを用いた有機電界発光素子 | |
CN102239161A (zh) | 1,3,5-三嗪衍生物、其生产方法及包括其作为构成成分的有机电致发光器件 | |
Tang et al. | Two novel orange cationic iridium (III) complexes with multifunctional ancillary ligands used for polymer light-emitting diodes | |
TW201204807A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
CN105051019A (zh) | 电子传输材料及使用该电子传输材料的有机电致发光元件 | |
He et al. | Light-emitting dyes derived from bifunctional chromophores of diarylamine and oxadiazole: Synthesis, crystal structure, photophysics and electroluminescence | |
JP5957518B2 (ja) | 希土類ユーロピウム錯体および発光材料としてのその使用 | |
Giridhar et al. | A systematic identification of efficiency enrichment between thiazole and benzothiazole based yellow iridium (III) complexes | |
JP2012126717A (ja) | 電子輸送材料およびこれを用いた有機電界発光素子 | |
TWI535823B (zh) | 有機金屬化合物、包含其之有機發光裝置、及其製備方法 | |
TWI594999B (zh) | 有機金屬錯合物及包含其之有機發光二極體 | |
TWI484020B (zh) | 含雙唑類配基的銥金屬錯合物 | |
TW201506017A (zh) | 用於電子輸送材料的化合物、電子輸送材料及使用其的有機電激發光元件 | |
JP6420889B2 (ja) | 化合物およびそれを用いた有機電子デバイス | |
TWI611004B (zh) | 鉑錯合物及使用其的有機發光二極體 | |
TW201927802A (zh) | 有機金屬化合物及包含其之有機發光裝置 | |
JP2013227251A (ja) | 電子輸送材料およびこれを用いた有機電界発光素子 | |
TWI498322B (zh) | 雙唑類鉑金屬發光錯合物 | |
TWI547497B (zh) | 有機金屬化合物、包含其之有機發光裝置及照明裝置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |