WO2017122516A1 - シクロメタル化イリジウム錯体の製造方法 - Google Patents
シクロメタル化イリジウム錯体の製造方法 Download PDFInfo
- Publication number
- WO2017122516A1 WO2017122516A1 PCT/JP2016/088394 JP2016088394W WO2017122516A1 WO 2017122516 A1 WO2017122516 A1 WO 2017122516A1 JP 2016088394 W JP2016088394 W JP 2016088394W WO 2017122516 A1 WO2017122516 A1 WO 2017122516A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- iridium
- iridium complex
- compound
- cyclometalated
- ligand
- Prior art date
Links
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 155
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 claims abstract description 92
- 150000002503 iridium Chemical class 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 51
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 150000002504 iridium compounds Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 126
- 125000004432 carbon atom Chemical group C* 0.000 claims description 110
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical group [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 10
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000010657 cyclometalation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RBNNPWUKDNRSMD-UHFFFAOYSA-N [Cl].[Ir] Chemical compound [Cl].[Ir] RBNNPWUKDNRSMD-UHFFFAOYSA-N 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 99
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 55
- -1 iridium halide Chemical class 0.000 description 38
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- 230000001815 facial effect Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 20
- 239000012300 argon atmosphere Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000005401 electroluminescence Methods 0.000 description 12
- 0 CCNCC[C@@](C)CCC* Chemical compound CCNCC[C@@](C)CCC* 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000539 dimer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- AZFHXIBNMPIGOD-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;iridium Chemical compound [Ir].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O AZFHXIBNMPIGOD-LNTINUHCSA-N 0.000 description 5
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical class C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 description 5
- 150000005360 2-phenylpyridines Chemical class 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- SHWNDUJCIYUZRF-UHFFFAOYSA-N imidazo[1,2-f]phenanthridine Chemical class C1=CC=C2N3C=CN=C3C3=CC=CC=C3C2=C1 SHWNDUJCIYUZRF-UHFFFAOYSA-N 0.000 description 4
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000002397 1-phenylpyrazoles Chemical class 0.000 description 3
- NYMLZIFRPNYAHS-UHFFFAOYSA-N 5-phenyl-1h-1,2,4-triazole Chemical class C1=NNC(C=2C=CC=CC=2)=N1 NYMLZIFRPNYAHS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FCEUOTOBJMBWHC-UHFFFAOYSA-N benzo[f]cinnoline Chemical class N1=CC=C2C3=CC=CC=C3C=CC2=N1 FCEUOTOBJMBWHC-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 3
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 150000004842 1-phenylimidazoles Chemical class 0.000 description 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 2
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical class C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 2
- XNCMQRWVMWLODV-UHFFFAOYSA-O 3-phenyl-1h-benzimidazol-3-ium Chemical class C=1NC2=CC=CC=C2[N+]=1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-O 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-O 3-phenyl-1h-imidazol-3-ium Chemical class C1=NC=C[NH+]1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-O 0.000 description 2
- RBJOTRVJJWIIER-UHFFFAOYSA-N 3-phenylisoquinoline Chemical class C1=CC=CC=C1C1=CC2=CC=CC=C2C=N1 RBJOTRVJJWIIER-UHFFFAOYSA-N 0.000 description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical class N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 2
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical class N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical class C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical class C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KBBSSGXNXGXONI-UHFFFAOYSA-N phenanthro[9,10-b]pyrazine Chemical class C1=CN=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 KBBSSGXNXGXONI-UHFFFAOYSA-N 0.000 description 2
- RIYPENPUNLHEBK-UHFFFAOYSA-N phenanthro[9,10-b]pyridine Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 RIYPENPUNLHEBK-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- YGRSXJJORLXYPT-UHFFFAOYSA-N 1-naphthalen-1-ylisoquinoline Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=NC=CC2=C1 YGRSXJJORLXYPT-UHFFFAOYSA-N 0.000 description 1
- IIMMYPSINSFUBX-UHFFFAOYSA-N 1-naphthalen-2-ylisoquinoline Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=C3)=NC=CC2=C1 IIMMYPSINSFUBX-UHFFFAOYSA-N 0.000 description 1
- AZQJQRTZFPAGNV-UHFFFAOYSA-N 1-phenylindazole Chemical class C12=CC=CC=C2C=NN1C1=CC=CC=C1 AZQJQRTZFPAGNV-UHFFFAOYSA-N 0.000 description 1
- VSKZGHVPGOMFAV-UHFFFAOYSA-N 1-pyridin-2-ylindole Chemical class C1=CC2=CC=CC=C2N1C1=CC=CC=N1 VSKZGHVPGOMFAV-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- RSNQVABHABAKEZ-UHFFFAOYSA-N 2,3-diphenylquinoxaline Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 RSNQVABHABAKEZ-UHFFFAOYSA-N 0.000 description 1
- DZYGAGZGZOLVCI-UHFFFAOYSA-N 2-(1-benzofuran-2-yl)pyridine Chemical class O1C2=CC=CC=C2C=C1C1=CC=CC=N1 DZYGAGZGZOLVCI-UHFFFAOYSA-N 0.000 description 1
- NRSBAUDUBWMTGL-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine Chemical class S1C2=CC=CC=C2C=C1C1=CC=CC=N1 NRSBAUDUBWMTGL-UHFFFAOYSA-N 0.000 description 1
- RIAJQFIZKHZWMP-UHFFFAOYSA-N 2-(furan-2-yl)pyridine Chemical class C1=COC(C=2N=CC=CC=2)=C1 RIAJQFIZKHZWMP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical class C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- VLRSADZEDXVUPG-UHFFFAOYSA-N 2-naphthalen-1-ylpyridine Chemical class N1=CC=CC=C1C1=CC=CC2=CC=CC=C12 VLRSADZEDXVUPG-UHFFFAOYSA-N 0.000 description 1
- IXVWMXLBXQAMMW-UHFFFAOYSA-N 2-naphthalen-1-ylquinoline Chemical class C1=CC=C2C(C3=NC4=CC=CC=C4C=C3)=CC=CC2=C1 IXVWMXLBXQAMMW-UHFFFAOYSA-N 0.000 description 1
- DBENTMPUKROOOE-UHFFFAOYSA-N 2-naphthalen-2-ylpyridine Chemical class N1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 DBENTMPUKROOOE-UHFFFAOYSA-N 0.000 description 1
- LPNLFJKYHYLXPE-UHFFFAOYSA-N 2-naphthalen-2-ylquinoline Chemical class C1=CC=CC2=NC(C3=CC4=CC=CC=C4C=C3)=CC=C21 LPNLFJKYHYLXPE-UHFFFAOYSA-N 0.000 description 1
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 description 1
- FIISKTXZUZBTRC-UHFFFAOYSA-N 2-phenyl-1,3-benzoxazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2O1 FIISKTXZUZBTRC-UHFFFAOYSA-N 0.000 description 1
- RQCBPOPQTLHDFC-UHFFFAOYSA-N 2-phenyl-1,3-oxazole Chemical class C1=COC(C=2C=CC=CC=2)=N1 RQCBPOPQTLHDFC-UHFFFAOYSA-N 0.000 description 1
- WYKHSBAVLOPISI-UHFFFAOYSA-N 2-phenyl-1,3-thiazole Chemical class C1=CSC(C=2C=CC=CC=2)=N1 WYKHSBAVLOPISI-UHFFFAOYSA-N 0.000 description 1
- QWNCDHYYJATYOG-UHFFFAOYSA-N 2-phenylquinoxaline Chemical class C1=CC=CC=C1C1=CN=C(C=CC=C2)C2=N1 QWNCDHYYJATYOG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- QLPKTAFPRRIFQX-UHFFFAOYSA-N 2-thiophen-2-ylpyridine Chemical class C1=CSC(C=2N=CC=CC=2)=C1 QLPKTAFPRRIFQX-UHFFFAOYSA-N 0.000 description 1
- YTTYNMGFPQYWKE-UHFFFAOYSA-N 3-naphthalen-1-ylisoquinoline Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=N3)=CC=CC2=C1 YTTYNMGFPQYWKE-UHFFFAOYSA-N 0.000 description 1
- CKUOKPSIXGRHSY-UHFFFAOYSA-N 3-naphthalen-2-ylisoquinoline Chemical class C1=CC=C2C=NC(C3=CC4=CC=CC=C4C=C3)=CC2=C1 CKUOKPSIXGRHSY-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- LUEYUHCBBXWTQT-UHFFFAOYSA-N 4-phenyl-2h-triazole Chemical class C1=NNN=C1C1=CC=CC=C1 LUEYUHCBBXWTQT-UHFFFAOYSA-N 0.000 description 1
- QCRWZQPISCKABP-UHFFFAOYSA-N 6-naphthalen-1-ylphenanthridine Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=NC3=CC=CC=C3C2=C1 QCRWZQPISCKABP-UHFFFAOYSA-N 0.000 description 1
- RBIMXMFIMHZNFR-UHFFFAOYSA-N 6-naphthalen-2-ylphenanthridine Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=C3)=NC3=CC=CC=C3C2=C1 RBIMXMFIMHZNFR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JDINBEDUGBFLEC-UHFFFAOYSA-N 9-pyridin-2-ylcarbazole Chemical class N1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JDINBEDUGBFLEC-UHFFFAOYSA-N 0.000 description 1
- OAPPEBNXKAKQGS-UHFFFAOYSA-N Benz[c]acridine Chemical class C1=CC=C2C3=NC4=CC=CC=C4C=C3C=CC2=C1 OAPPEBNXKAKQGS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UBKRQQXVQDRPEU-UHFFFAOYSA-K C(C)S(=O)(=O)[O-].[Ir+3].C(C)S(=O)(=O)[O-].C(C)S(=O)(=O)[O-] Chemical compound C(C)S(=O)(=O)[O-].[Ir+3].C(C)S(=O)(=O)[O-].C(C)S(=O)(=O)[O-] UBKRQQXVQDRPEU-UHFFFAOYSA-K 0.000 description 1
- YZMWPGNLYDZKGP-UHFFFAOYSA-K C(CCC)S(=O)(=O)[O-].[Ir+3].C(CCC)S(=O)(=O)[O-].C(CCC)S(=O)(=O)[O-] Chemical compound C(CCC)S(=O)(=O)[O-].[Ir+3].C(CCC)S(=O)(=O)[O-].C(CCC)S(=O)(=O)[O-] YZMWPGNLYDZKGP-UHFFFAOYSA-K 0.000 description 1
- JGAJHOGTSITVOQ-UHFFFAOYSA-K C1(=CC=CC=C1)S(=O)(=O)[O-].[Ir+3].C1(=CC=CC=C1)S(=O)(=O)[O-].C1(=CC=CC=C1)S(=O)(=O)[O-] Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].[Ir+3].C1(=CC=CC=C1)S(=O)(=O)[O-].C1(=CC=CC=C1)S(=O)(=O)[O-] JGAJHOGTSITVOQ-UHFFFAOYSA-K 0.000 description 1
- UXMXEMPDNOEBQT-UHFFFAOYSA-K CC1=CC=C(C=C1)S(=O)(=O)[O-].[Ir+3].CC1=CC=C(C=C1)S(=O)(=O)[O-].CC1=CC=C(C=C1)S(=O)(=O)[O-] Chemical compound CC1=CC=C(C=C1)S(=O)(=O)[O-].[Ir+3].CC1=CC=C(C=C1)S(=O)(=O)[O-].CC1=CC=C(C=C1)S(=O)(=O)[O-] UXMXEMPDNOEBQT-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXZBAEYSECUITM-UHFFFAOYSA-K FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.[Ir+3].FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.[Ir+3].FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F PXZBAEYSECUITM-UHFFFAOYSA-K 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZNJYTUSWSVUQTP-UHFFFAOYSA-J [Ir+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ir+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZNJYTUSWSVUQTP-UHFFFAOYSA-J 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- MHDLAWFYLQAULB-UHFFFAOYSA-N anilinophosphonic acid Chemical compound OP(O)(=O)NC1=CC=CC=C1 MHDLAWFYLQAULB-UHFFFAOYSA-N 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- SEXRCKWGFSXUOO-UHFFFAOYSA-N benzo[a]phenazine Chemical class C1=CC=C2N=C3C4=CC=CC=C4C=CC3=NC2=C1 SEXRCKWGFSXUOO-UHFFFAOYSA-N 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- NBAUUSKPFGFBQZ-UHFFFAOYSA-N diethylaminophosphonic acid Chemical compound CCN(CC)P(O)(O)=O NBAUUSKPFGFBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- LFRHVXZQEHAFPS-UHFFFAOYSA-K iridium(3+) 2,2,2-trifluoroacetate Chemical compound FC(C(=O)[O-])(F)F.[Ir+3].FC(C(=O)[O-])(F)F.FC(C(=O)[O-])(F)F LFRHVXZQEHAFPS-UHFFFAOYSA-K 0.000 description 1
- YZDLOROLAIVFRY-UHFFFAOYSA-K iridium(3+) methanesulfonate Chemical compound CS(=O)(=O)[O-].[Ir+3].CS(=O)(=O)[O-].CS(=O)(=O)[O-] YZDLOROLAIVFRY-UHFFFAOYSA-K 0.000 description 1
- QIEABXIHCMILKG-UHFFFAOYSA-K iridium(3+);trifluoromethanesulfonate Chemical compound [Ir+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F QIEABXIHCMILKG-UHFFFAOYSA-K 0.000 description 1
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002668 lysine derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- GUZBPGZOTDAWBO-UHFFFAOYSA-N phenanthro[9,10-b]quinoline Chemical class C1=CC=C2C3=CC4=CC=CC=C4N=C3C3=CC=CC=C3C2=C1 GUZBPGZOTDAWBO-UHFFFAOYSA-N 0.000 description 1
- KHPYJVQRBJJYSF-UHFFFAOYSA-N phenanthro[9,10-b]quinoxaline Chemical class C1=CC=C2C3=NC4=CC=CC=C4N=C3C3=CC=CC=C3C2=C1 KHPYJVQRBJJYSF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)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
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoric acid amide group Chemical group P(N)(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 125000005030 pyridylthio group Chemical group N1=C(C=CC=C1)S* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 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
- 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
- 229920002554 vinyl polymer Polymers 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
-
- 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
- C09K2211/1018—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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three 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
-
- 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
Definitions
- the present invention relates to a technique for producing a cyclometalated iridium complex applicable to an organic electroluminescence (EL) element, an organic electrochemiluminescence (ECL) element, a luminescence sensor, a photosensitizing dye, a photocatalyst, various light sources, and the like. .
- EL organic electroluminescence
- ECL organic electrochemiluminescence
- luminescence sensor a luminescence sensor
- photosensitizing dye a photocatalyst
- various light sources and the like.
- the cyclometalated iridium complex is a general term for an organic iridium complex in which a polydentate ligand is coordinated cyclically to an iridium atom and has at least one iridium-carbon bond.
- a polydentate ligand is coordinated cyclically to an iridium atom and has at least one iridium-carbon bond.
- tris (2-phenylpyridine) And iridium (Ir (ppy) 3 ) and the like tris (2-phenylpyridine) And iridium (Ir (ppy) 3 ) and the like.
- phosphorescent materials such as organic EL devices. Used as An organic EL element using a phosphorescent material is 3 to 4 times higher in luminous efficiency than an organic EL element using a conventional fluorescent material, and thus is an indispensable material for improving the efficiency and energy saving of the organic EL element. .
- Cyclometalated iridium complexes include biscyclometalated iridium complexes in which two aromatic heterocyclic bidentate ligands are coordinated to the iridium atom, and three aromatic heterocyclic bidentate ligands to the iridium atom. Triscyclometalated iridium complexes and the like. Of these, the triscyclometalated iridium complex has particularly high thermal stability, and can be expected to have a long lifetime when applied to an organic EL device or the like.
- iridium trichloride is reacted with an aromatic heterocyclic bidentate ligand such as 2-phenylpyridine (ppy) and synthesized in one step.
- aromatic heterocyclic bidentate ligand such as 2-phenylpyridine (ppy)
- Non-Patent Document 1 a chlorine-bridged dimer (Chemical Formula 3) is obtained as a main product, and a desired cyclometalated iridium complex cannot be synthesized with high yield. Furthermore, the cyclometalated iridium complex obtained by one-step synthesis using iridium trichloride as a raw material has a problem that chlorine derived from iridium trichloride remains. It has been pointed out that the residual chlorine content adversely affects the light emission characteristics when applied to an organic EL element (see Patent Document 1).
- a method for producing a cyclometalated iridium complex examples include tris (2,4-pentandionato) iridium (III) (hereinafter also referred to as Ir (acac) 3 ) and 2-phenylpyridine (ppy).
- Ir (acac) 3 tris (2,4-pentandionato) iridium
- ppy 2-phenylpyridine
- a method of obtaining a cyclometalated iridium complex in a single step by reacting with an aromatic heterocyclic bidentate ligand such as) is also known (Chemical Formula 4, Non-Patent Document 2).
- Non-Patent Document 2 is a method using Ir (acac) 3 which is a non-chlorine iridium raw material as a raw material, and the cyclometalated iridium complex as a product is added with a chlorine content derived from the iridium raw material.
- Ir (acac) 3 has a problem that it is thermally stable and poor in reactivity, and the synthesis yield of the cyclometalated iridium complex is low.
- a method for producing a cyclometalated iridium complex there is also a method of obtaining a cyclometalated iridium complex in one step by reacting iridium acetate with an aromatic heterocyclic bidentate ligand (Chemical Formula 5, Patent) Reference 2).
- Iridium acetate which is a non-chlorine iridium raw material, is reactive and has a characteristic that a cyclometalated iridium complex can be obtained even at a reaction temperature of 200 ° C. or lower. Therefore, there is little concern about a decrease in yield due to an unexpected decomposition reaction in a reaction under a high temperature condition. Moreover, since a non-chlorine type iridium raw material is used, there is no residual chlorine.
- the triscyclometalated iridium complex which is particularly suitable as a phosphorescent material such as an organic EL element, includes facial isomers and meridional isomers, which are geometric isomers. Exists. Among these, it is a facial body that has high luminous efficiency and is known to be desirable as a luminescent material. According to the present inventors, when a triscyclometalated iridium complex is produced using iridium acetate as a raw material, an undesirable meridional body tends to be easily produced as a luminescent material.
- the present invention provides a cyclometalated iridium complex that can be suitably used as a light-emitting material such as an organic EL element in a one-step synthesis reaction from a non-chlorine iridium raw material at a lower temperature.
- the purpose is to provide a technique that can be obtained with high purity.
- a method for easily producing a facial body when producing a triscyclometalated iridium complex is disclosed.
- the present inventors have intensively studied iridium raw materials for developing a method for producing a cyclometalated iridium complex from non-chlorine iridium raw materials in one step.
- the present inventors have found that the above-described problems can be solved by applying non-halogenated iridium having a conjugated base of a strong acid as a ligand as a non-chlorine iridium raw material.
- a facial cyclometalated iridium complex suitable as a phosphorescent material for an organic EL device can be produced with higher purity than when iridium acetate, which is a conventional non-chlorine iridium raw material, is used. It was.
- the present invention provides a method for producing a cyclometalated iridium complex by reacting a raw material comprising an iridium compound with an aromatic heterocyclic bidentate ligand capable of forming an iridium-carbon bond.
- a process for producing a cyclometalated iridium complex comprising reacting non-halogenated iridium having a conjugate base of a strong acid as a ligand.
- the non-halogenated iridium having a strong acid conjugate base as a ligand is an iridium compound having a strong acid conjugate base as a ligand and not an iridium halide.
- examples of iridium halides excluded in the present invention include JP-A-2015-189687, JP-A-2014-005223, JP-A-2007-091718, JP-A-2014-505041, JP-A-2007-513159, and the like. There are iridium compounds described in.
- iridium halide examples include iridium (III) chloride, iridium bromide (III), iridium iodide (III), iridium chloride (IV) acid, iridium bromide (IV) acid, and iridium iodide (IV).
- acids and salts thereof ammonium salts, potassium salts, sodium salts, etc.
- hydrates examples thereof include acids and salts thereof (ammonium salts, potassium salts, sodium salts, etc.) and hydrates.
- the strong acid is an acid having a pKa of 3 or less, preferably an acid having a pKa of 2 or less, and more preferably an acid having a pKa of 1 or less.
- examples of such acids include nitric acid, sulfuric acid, trifluoroacetic acid, arylsulfonic acid (p-toluenesulfonic acid, benzenesulfonic acid, etc.), perfluoroalkylsulfonic acid, (trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid) Etc.), alkyl sulfonic acids (methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, etc.).
- nitric acid or sulfuric acid is preferable, and nitric acid is more preferable.
- non-halogenated iridium having a strong acid conjugate base as a ligand include iridium nitrate, iridium sulfate, iridium trifluoroacetate, iridium p-toluenesulfonate, iridium benzenesulfonate, and iridium trifluoromethanesulfonate.
- Iridium nonafluorobutanesulfonate iridium methanesulfonate, iridium ethanesulfonate, and iridium butanesulfonate, preferably iridium nitrate or iridium sulfate, and more preferably iridium nitrate.
- the valence of iridium in non-halogenated iridium having a strong acid conjugate base as a ligand is preferably trivalent or tetravalent, and more preferably tetravalent. Further, a mixture of trivalent and tetravalent may be used.
- iridium nitrate represented by Ir (NO 3 ) 3 and Ir (NO 3 ) 4 , and any of these or a mixture thereof can be applied.
- Ir (NO 3 ) 2 (OH) 2 [Ir (NO 3 ) 2 (OH) 2 ] + , [Ir (NO 3 ) 2 (H 2 O) 2 ] 2+ and an iridium compound having water as a ligand may be contained.
- [(NO 3) 2 Ir (OH) 2 Ir (NO 3) 2] with a hydroxide ion ligand may contain a multi-nuclear iridium compound crosslinked represented by like.
- a preferable method for producing iridium nitrate includes, for example, a method via iridium hydroxide described in JP-A-2001-106536.
- examples of the structure of iridium sulfate preferably used in the present invention include Ir 2 (SO 4 ) 3 and Ir (SO 4 ) 2 .
- the non-halogenated iridium having a strong acid conjugate base as a ligand used in the method for producing a cyclometalated iridium complex according to the present invention can be used in a solid state.
- the solid state is not particularly limited, and examples thereof include a lump shape, a small piece shape, and a granular shape.
- the non-halogenated iridium may contain crystal water or a crystal solvent.
- the non-halogenated iridium having a strong acid conjugate base used in the present invention as a ligand may be dissolved or dispersed in a solvent such as water or alcohol.
- a solvent such as water or alcohol.
- water is particularly preferable, and it is more preferable that the solvent is dissolved or dispersed in water.
- the aqueous solution is preferably a strongly acidic solution having a pH of 0 to 3. This is because if the pH exceeds 3, precipitation (IrO 2 ⁇ nH 2 O) may gradually occur with time.
- a base sodium hydroxide, potassium hydroxide, sodium bicarbonate, etc.
- a base sodium hydroxide, potassium hydroxide, sodium bicarbonate, etc.
- the iridium concentration of the solution containing non-halogenated iridium having a strong acid conjugate base as a ligand is preferably 0.01 to 99.9 wt%, more preferably 0.1 to 90 wt%, and 1 to 70 wt%. Particularly preferred is 5 to 50% by weight.
- the residual halogen concentration contained in the non-halogenated iridium having a strong acid conjugate base as a ligand is preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less.
- the aromatic heterocyclic bidentate ligand used in the present invention is an aromatic heterocyclic bidentate ligand capable of forming an iridium-carbon bond.
- An aromatic heterocyclic bidentate ligand is an aromatic heterocyclic bidentate ligand that forms one iridium-nitrogen bond and one iridium-carbon bond, or an aromatic that forms two iridium-carbon bonds.
- An aromatic heterocyclic bidentate ligand that forms one iridium-nitrogen bond and one iridium-carbon bond is more preferable.
- the aromatic heterocyclic bidentate ligand is specifically an aromatic heterocyclic bidentate ligand represented by the general formula (1).
- this invention makes nonaromatic iridium which has the conjugate base of the strong acid demonstrated above as a ligand react with the aromatic heterocyclic bidentate ligand represented by General formula (1), General formula (1)
- the cyclometalated iridium complex represented by (2) can be produced.
- N represents a nitrogen atom.
- C represents a carbon atom.
- Z 1 and Z 2 each independently form a 5-membered ring or a 6-membered ring. Represents a necessary group of nonmetallic atoms, the ring formed may form a condensed ring with another ring, L 1 represents a single bond or a divalent group, Y 1 represents a nitrogen atom or a carbon atom, respectively.
- Q 1 represents that a carbon atom and Y 1 are bonded by a single bond, and when Y 1 is a carbon atom, Q 1 is a carbon atom and Y 1. And are bonded by a double bond.
- the present invention also provides a non-halogenated iridium having the above-described strong acid conjugate base as a ligand, an aromatic heterocyclic bidentate ligand represented by the above general formula (1), and a general formula (3 And a cyclometalated iridium complex represented by the general formula (4) can be produced.
- N represents a nitrogen atom.
- C represents a carbon atom.
- Z 1 and Z 2 each independently form a 5-membered ring or a 6-membered ring. Represents a necessary group of nonmetallic atoms, the ring formed may form a condensed ring with another ring, L 1 represents a single bond or a divalent group, Y 1 represents a nitrogen atom or a carbon atom, respectively.
- Q 1 represents that a carbon atom and Y 1 are bonded by a single bond, and when Y 1 is a carbon atom, Q 1 is a carbon atom and Y 1.
- Z 3 and Z 4 each independently represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring. even better .L 2 also form a condensed ring with another ring represents a single bond or a divalent represents a group .
- Y 2 are each nitrogen or carbon atom. When 2 is a nitrogen atom, Q 2 when .Y 2 indicating that the carbon atom and Y 2 are linked by a single bond is a carbon atom, Q 2 has and the Y 2 carbon atoms doubly
- aromatic heterocyclic bidentate ligand used in the present invention include those having structures shown in the following structural examples 1 to 3. Further, those represented by the general formulas (5) to (12) can be mentioned.
- the aromatic heterocyclic bidentate ligands having the structures represented by the general formulas (5) to (12) are preferable, and among these, the general formulas (5), (7), (10), or What has the structure shown by (11) is more preferable, and what has the structure shown by General formula (5), (7) or (10) is especially preferable.
- * represents a binding site with iridium.
- R and R 1 to R 73 are a hydrogen atom or a substituent.
- substituents include the following substituents.
- An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, Iso-propyl, tert-butyl, n-octyl, n -Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.)
- An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.)
- An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl, 3-pentynyl, etc.)
- An aryl group (preferably having 6
- Heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.)
- Acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl, etc.)
- An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.)
- An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof
- Acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy).
- Acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino).
- An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino).
- Aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino)
- a sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino).
- a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.
- a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.)
- An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio).
- Arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio).
- Heterocyclic thio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio And 2-benzthiazolylthio.)
- a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl).
- a sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.)
- a ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido).
- a phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide).
- halogen atom eg fluorine atom, chlorine atom, bromine atom, iodine atom
- a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl).
- a silyloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy and triphenylsilyloxy).
- an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, a trifluoromethyl group, or a heterocyclic group particularly preferably It is an alkyl group, an aryl group, a halogen atom, a cyano group, a trifluoromethyl group, or a heterocyclic group, and more preferably an alkyl group, an aryl group, or a halogen atom. Desirable ranges for these substituents are as described above, and they may be further substituted with the substituents defined by R and R 1 to R 73 described above.
- aromatic heterocyclic bidentate ligand based on the above structural formula includes the following ligands. That is, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative, 1-phenyl-1H-indazole derivative, 2-phenylbenzothiazole derivative, 2-phenylthiazole derivative, 2-phenylbenzoxazole derivative, 2-phenyloxazole derivative, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine Derivatives, 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 9 -(
- aromatic heterocyclic bidentate ligand among the above, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 1-phenylpyrazole derivative, 7,8- Benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 6-phenylphenanthridine derivatives 2-phenylquinoxaline derivative, 2,3-diphenylquinoxaline derivative, 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 2-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltria Derivatives, 5-phenyltetrazole derivatives, 5-phenyl-1,2,4-triazole derivative
- 2-phenylpyridine derivative 7,8-benzoquinoxaline derivative, 1-phenylisoquinoline derivative, 1-phenylpyrazole derivative, 2-phenylimidazole derivative, 5-phenyl-1,2,4-triazole derivative, or
- an imidazo [1,2-f] phenanthridine derivative is preferable, and a 2-phenylpyridine derivative, a 1-phenylisoquinoline derivative, a 2-phenylimidazole derivative, or an imidazo [1,2-f] phenanthridine Derivatives are more particularly preferred.
- the non-halogenated iridium having the strong acid conjugate base described above as a ligand is reacted with the above-described aromatic heterocyclic bidentate ligand. Is done.
- the above reaction can be performed in an atmosphere of air or an inert gas (such as nitrogen or argon), and is preferably performed in an inert gas atmosphere.
- an inert gas such as nitrogen or argon
- a solvent may be added to the reaction system for the synthesis reaction in order to make the above reaction proceed more smoothly.
- Solvents added to the reaction system include saturated aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ketones, amides, esters, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing aromatic compounds, ethers And various organic solvents such as nitriles, alcohols and ionic liquids, and alcohols (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 30 carbon atoms). Is more preferable.
- ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, etc. Can be mentioned.
- ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol are preferable. It is also preferable to use a mixed solvent containing two or more of the above solvents.
- the solvent preferably has a boiling point at normal pressure of 100 ° C. to 400 ° C., more preferably 150 ° C. to 350 ° C., and particularly preferably 180 ° C. to 300 ° C.
- the concentration of the non-halogenated iridium having a strong acid conjugate base as a ligand is not particularly limited, but is 0.001 mol / L to 10.0 mol. / L is preferable, 0.001 mol / L to 1.0 mol / L is more preferable, 0.01 mol / L to 1.0 mol / L is particularly preferable, and 0.05 mol / L to 0.5 mol is preferable. / L is most preferred.
- the reaction temperature is preferably 100 ° C to 300 ° C, more preferably 150 ° C to 250 ° C, particularly preferably 160 ° C to 220 ° C, and particularly preferably 170 ° C to 200 ° C.
- a cyclometalated iridium complex can be synthesized even under low temperature conditions of 200 ° C. or lower.
- the reaction time is preferably 1 to 100 hours, more preferably 3 to 80 hours, and particularly preferably 5 to 50 hours.
- the heating means is not particularly limited. Specifically, an oil bath, a sand bath, a mantle heater, a block heater, external heating by a heat circulation jacket, heating by microwave irradiation, or the like can be used.
- the synthesis of the cyclometalated iridium complex is usually carried out at normal pressure, but may be carried out under pressure or under reduced pressure as necessary.
- the amount of the aromatic heterocyclic bidentate ligand used is not particularly limited, but it is 3 to 100 times mol of non-halogenated iridium having a strong acid conjugate base as a ligand. 3 to 50 times mol is more preferable, 3 to 30 times mol is particularly preferable, and 3 to 10 times mol is most preferable.
- the cyclometalated iridium complex obtained by the synthesis method described above can be used as a high-purity product without any purification after purification by a general post-treatment method, if necessary.
- a post-treatment method for example, extraction, cooling, crystallization by adding water or an organic solvent, an operation of distilling off the solvent from the reaction mixture, and the like can be performed alone or in combination.
- a purification method recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.
- the method for producing a cyclometalated iridium complex according to the present invention is suitable for producing a biscyclometalated iridium complex or a triscyclometalated iridium complex. In particular, it is suitable for production of a triscyclometalated iridium complex.
- Specific examples of these cyclometalated iridium complexes include JP2007-224025, JP2006-290891, JP2006-213723, JP2006-111623, and JP2006-104201.
- JP-A-2006-063080 JP-T 2009-541431, JP-T 2009-526071, JP-T 2008-505076, JP-T 2007-513159, JP-T 2007-513158 JP-T 2002-540572, JP-T 2009-544167, JP-T 2009-522228, JP-T 2008-514005, JP-T 2008-504342, JP-T 2007-504272, JP-T Table 2006-523231, Table 2005-516040 JP is described in WO 2010/086089 pamphlet or the like.
- the triscyclometalated iridium complex includes a homoleptic iridium complex in which three cyclometalated ligands are the same (for example, a compound of the general formula (2)) and three cyclometalated ligands. Can be classified into heteroleptic iridium complexes (for example, compounds of the general formula (4)). In the present invention, both a homoleptic iridium complex and a heteroleptic iridium complex can be produced as the triscyclometalated iridium complex.
- non-halogenated iridium having a strong acid conjugate base as a ligand and a single aromatic heterocyclic ring 2 An iridium complex can be obtained by reacting a bidentate ligand.
- different heteroaromatic bidentate ligands are introduced in order to produce heteroleptic iridium complexes, non-halogenated iridiums having strong acid conjugate bases as ligands and a plurality of types of aromatic heterocycles.
- a ring bidentate ligand may be reacted, or a non-halogenated iridium having a strong acid conjugate base as a ligand is reacted with an aromatic heterocyclic bidentate ligand, followed by a different aromatic heterocycle.
- a desired iridium complex can be obtained by reacting with a ring bidentate ligand.
- a homoleptic iridium complex and a heteroleptic iridium complex are produced simultaneously, they can be separated and purified using column chromatography or the like and isolated from each other.
- the present invention is also useful for the production of biscyclometalated iridium complexes.
- non-halogenated iridium having a conjugate base of a strong acid as a ligand is reacted with an aromatic heterocyclic bidentate ligand.
- an iridium complex can be obtained by reacting with an auxiliary ligand ( ⁇ -diketone ligand, picolinic acid ligand, etc.).
- the present invention is particularly useful for the production of triscyclometalated iridium complexes.
- the triscyclometalated iridium complex has a three-dimensional structure in which three ⁇ -diketone ligands are arranged in an octahedral shape with an iridium metal as a center. Due to this three-dimensional structure, the triscyclometalated iridium complex has two types of geometric isomers, a facial isomer and a meridional isomer.
- Facial and meridional isomers are nomenclature of hexacoordinate octahedral complex isomers and are described in Organometallic Chemistry-Fundamentals and Applications-Akio Yamamoto (Touhuabo), p.143.
- a facial body is desirable as a light emitting material having high luminous efficiency.
- a facial triscyclometalated iridium complex can be efficiently produced by using non-halogenated iridium having a strong acid conjugate base as a ligand. The reason for this is not yet clear, but the present inventor thinks as follows.
- a facial cyclometalated iridium complex is thermodynamically more advantageous than a meridional complex and is easily formed by a high-temperature reaction.
- a meridional cyclometalated iridium complex is kinetically advantageous and easily formed by a low-temperature reaction.
- a meridional body advantageous in terms of kinetics is likely to be generated because the acetic acid ligand is easily detached at a low temperature.
- the geometric isomer in the cyclometalated iridium complex can be identified by various instrumental analyzes such as 1 H-NMR. Each content of the facial and meridional forms can be quantified using 1 H-NMR, high performance liquid chromatography or the like.
- the present invention is not limited to the production of a triscyclometalated iridium complex or a biscyclometalated iridium complex.
- the present invention has the advantage that it can efficiently produce a tris-cyclometalated iridium complex in a facial form, but it also has the advantage of making it possible to produce a cyclometalated iridium complex having no halogen residue under relatively low temperature conditions. There is also. This is because these merits can also be enjoyed in the production of cyclometalated iridium complexes other than triscyclometalated iridium complexes.
- the present invention unlike conventional iridium halides, by using non-halogenated iridium having a conjugate base of a strong acid as a ligand, no halogen-bridged dimer is formed at all, and the desired cyclometal An iridium iodide complex can be produced efficiently.
- the cyclometalated iridium complex obtained by using the present invention does not contain a halogen (such as chlorine) derived from an iridium raw material.
- the cyclometalated iridium complex can be produced under milder conditions than when tris (2,4-pentanedionato) iridium (III) is used.
- the present invention can efficiently produce a facial triscyclometalated iridium complex useful as a phosphorescent material, as compared with the conventional method using iridium acetate.
- iridium nitrate or iridium sulfate is used as a non-halogenated iridium having a conjugate base of a strong acid as a ligand, and a plurality of types of aromatic heterocyclic bidentate ligands are reacted to form a cyclometalated iridium complex ( Of the iridium compounds listed in Chemical formula 21, Compound (1), Compound (4), Compound (5), Compound (10), Compound (12), Compound (14), Compound (16), Compound of Formula 23 ( 34) to (39)) were produced.
- iridium nitrate as an iridium raw material of the cyclometalated iridium complex was synthesized based on JP-A-2001-106536, and then the nitric acid was distilled off under reduced pressure and dried to obtain a black solid.
- the aqueous iridium nitrate solution was manufactured by adding water and dissolving this black solid of iridium nitrate.
- the pH of this iridium nitrate aqueous solution was 0.54.
- the residual chlorine concentration contained in the iridium nitrate aqueous solution was 160 ppm.
- This aqueous iridium nitrate solution was used in Examples 1 to 16 and 19.
- the black solid of the iridium nitrate manufactured above was used in Examples 17 and 18.
- Example 1 Synthesis of Compound (1) 403.8 mg of iridium nitrate aqueous solution (iridium content: 9.52 wt%), 186.2 mg of compound (A), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 78%.
- Example 2 Synthesis of compound (4) 403.8 mg of iridium nitrate aqueous solution (iridium content: 9.52 wt%), 203.1 mg of compound (B), and 5 ml of ethylene glycol were heated at 180 ° C for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and extracted with dichloromethane. The oil layer was collected and concentrated under reduced pressure, and the resulting solid was recrystallized using dichloromethane and methanol. The compound was identified using 1 H-NMR and confirmed to be compound (4). The isolated yield of compound (4) was 70%.
- Example 3 Synthesis of compound (5) 403.8 mg of iridium nitrate aqueous solution (iridium content: 9.52 wt%), 207.8 mg of compound (C), and 5 ml of ethylene glycol were heated at 180 ° C for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The product was purified by silica gel column chromatography (eluent: dichloromethane). The compound was identified using 1 H-NMR and confirmed to be compound (5). The isolated yield of compound (5) was 75%.
- Example 4 Synthesis of Compound (10) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%), 246.3 mg of Compound (D), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (10). The isolated yield of compound (10) was 80%.
- Example 5 Synthesis of Compound (12) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%), 313.6 mg of Compound (E), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (12). The isolated yield of compound (12) was 75%.
- Example 7 Synthesis of Compound (16) 807.6 mg of iridium nitrate aqueous solution (iridium content: 9.52 wt%), 528.0 mg of compound (G), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (16). The isolated yield of compound (16) was 60%.
- Example 8 Synthesis of Compound (36) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%), 277.6 mg of Compound (H), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (36). The isolated yield of compound (36) was 80%.
- Example 9 Synthesis of Compound (39) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%), 294.4 mg of Compound (I), and 5 ml of ethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. Further purification was performed by silica gel column chromatography (eluent: dichloromethane). The compound was identified using 1 H-NMR and confirmed to be compound (39). The isolated yield of compound (39) was 70%.
- Example 10 Synthesis of Compound (1) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%), 186.2 mg of Compound (A), and 5 ml of ethylene glycol were heated at 150 ° C. for 34 hours in an argon atmosphere. Reacted. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 70%.
- Example 11 Synthesis of compound (1) After adding water to 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%) and diluting 10 times, 186.2 mg of compound (A) and 50 ml of ethylene glycol were added. The reaction was heated at 180 ° C. for 17 hours under an argon atmosphere. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 60%.
- Example 12 Synthesis of Compound (1) Iridium nitrate aqueous solution (iridium content: 9.52 wt%) 403.8 mg, Compound (A) 186.2 mg, and 5 ml of diethylene glycol were heated at 180 ° C. for 17 hours in an argon atmosphere. did. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 60%.
- Example 13 Synthesis of Compound (1) 403.8 mg of an iridium nitrate aqueous solution (iridium content: 9.52 wt%) was weighed and the solution was distilled off under reduced pressure using an evaporator. Then, 186.2 mg of compound (A) and diethylene glycol were used. 5 ml was added, and the mixture was reacted by heating at 180 ° C. for 17 hours under an argon atmosphere. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 75%.
- Example 15 Synthesis of Compounds (1), (10), (34) and (35) 403.8 mg of an aqueous iridium nitrate solution (iridium content: 9.52 wt%), 31.0 mg of Compound (A), and Compound (D) 205. 3 mg and 5 ml of ethylene glycol were heated and reacted at 180 ° C. for 17 hours in an argon atmosphere. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. The yield of the obtained solid was 110 mg.
- Example 17 Synthesis of Compound (1) 71.9 mg of iridium nitrate black solid (iridium content 53.48 wt%), 109.0 mg of compound (A), and 5 ml of ethylene glycol at 180 ° C. under argon atmosphere The reaction was heated for an hour. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. Furthermore, the origin impurities were removed using silica gel chromatography (eluent: dichloromethane) to obtain a yellow solid. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 93%.
- Example 18 Synthesis of Compound (10) 71.0 mg of iridium nitrate black solid (iridium content: 54.12 wt%), 143.5 mg of Compound (D), and 5 ml of ethylene glycol were added at 180 ° C. under an argon atmosphere. The reaction was heated for an hour. The reaction mixture was cooled to room temperature and methanol was added. The precipitated solid was collected by filtration and washed with methanol. Further, the origin impurities were removed using silica gel chromatography (eluent: dichloromethane) to obtain a red solid. The compound was identified using 1 H-NMR and confirmed to be compound (10). The isolated yield of compound (10) was 73%.
- Example 19 From the above examination results in Examples 1 to 19, it is possible to produce a cyclometalated iridium complex by using non-halogenated iridium having a strong acid conjugate base as a ligand or an aqueous solution thereof. It was revealed.
- a homoleptic iridium complex such as compound (1) can be produced alone (Examples 1 to 13, Example 17, and Example 18). It was also confirmed that a homoleptic iridium complex and a heteroleptic iridium complex can be produced simultaneously by reacting a non-halogenated iridium as a ligand with a plurality of aromatic heterocyclic bidentate ligands (Examples 14 to Example 16 and Example 19).
- iridium (III) chloride which is a conventional iridium raw material, was used, but it was revealed that the desired cyclometalated iridium complex could not be obtained at all. This is because it was affected by the formation of chlorine-crosslinked dimers. It was confirmed that by using a non-halogen (non-chlorine) raw material as in each Example, a desired cyclometalated iridium complex can be produced without producing a chlorine-bridged dimer.
- the purity of the facial product of the cyclometalated iridium complex as a product was precisely analyzed by HPLC, and compared with the case where iridium acetate was used as the iridium raw material.
- the same study was performed in the case where iridium sulfate was applied as non-halogenated iridium having a conjugate base of a strong acid as a ligand.
- Example 20 Compound (1) obtained in Example 1 was subjected to HPLC (Prominence, manufactured by Shimadzu Corporation), column: normal phase silica gel, mobile phase: mixed solvent of THF (40%) and hexane (60%), detection wavelength: 300 nm). As a result of analysis, the production ratio of facial body and meridional body was 99.64: 0.36 (peak area ratio).
- Example 21 Compound (10) obtained in Example 4 was subjected to HPLC (Prominence, manufactured by Shimadzu Corporation), column: normal phase silica gel, mobile phase: mixed solvent of THF (40%) and hexane (60%), detection wavelength: 300 nm). As a result of analysis, the production ratio of facial body and meridional body was 99.57: 0.43 (peak area ratio).
- Example 22 Synthesis of compound (1) by iridium sulfate
- iridium sulfate (IV) n hydrate was used, and the other methods were the same as in Example 1.
- compound (1) was produced.
- the used iridium sulfate (IV) n hydrate is a commercial product (distributor: Mitsuwa Chemical Industry Co., Ltd.).
- the obtained compound (1) was analyzed by HPLC (Prominence, manufactured by Shimadzu Corporation, column: normal phase silica gel, mobile phase: mixed solvent of THF (40%) and hexane (60%), detection wavelength: 300 nm). As a result, the production ratio of facial body and meridional body was 99.97: 0.03 (peak area ratio).
- Example 5 The reaction was performed in the same manner as in Example 1 except that iridium acetate (manufactured by ChemPur GmbH) was used instead of the iridium nitrate aqueous solution of Example 1.
- the compound was identified using 1 H-NMR and confirmed to be compound (1).
- the isolated yield of compound (1) was 75%.
- the obtained compound (1) was analyzed by HPLC (Prominence, manufactured by Shimadzu Corporation), column: normal phase silica gel, mobile phase: mixed solvent of THF (40%) and hexane (60%), detection wavelength: 300 nm),
- the production ratio of facial body and meridional body was 83.59: 16.41 (peak area ratio).
- Example 6 The reaction was conducted in the same manner as in Example 4 except that iridium acetate (manufactured by ChemPur GmbH) was used in place of the iridium nitrate aqueous solution of Example 4. The compound was identified using 1 H-NMR and confirmed to be compound (10). The isolated yield of compound (10) was 75%. The obtained compound (10) was analyzed by HPLC (Prominence, manufactured by Shimadzu Corporation), column: normal phase silica gel, mobile phase: mixed solvent of THF (40%) and hexane (60%), detection wavelength: 300 nm), The production ratio of facial body and meridional body was 99.24: 0.76 (peak area ratio).
- Example 20 and Comparative Example 5 reveals that the purity of the facial body of compound (1) is higher and superior in the production method of Example 20. Further, as in Example 22, even when iridium (IV) sulfate n hydrate is applied, a cyclometalated iridium complex containing a highly pure facial product can be obtained. Similarly, when Example 21 and Comparative Example 6 are compared, it can be seen that the facial body purity of the compound (10) is higher and superior in the production method of Example 21.
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Abstract
Description
・アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、2-ブテニル、3-ペンテニル等が挙げられる。)
・アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばプロパルギル、3-ペンチニル等が挙げられる。)
・アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニル等が挙げられる。)
・アミノ基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノ等が挙げられる。)
・アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシ等が挙げられる。)
・アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシ等が挙げられる。)
・ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシ等が挙げられる。)
・アシル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイル等が挙げられる。)
・アルコキシカルボニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニル、エトキシカルボニル等が挙げられる。)
・アリールオキシカルボニル基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニル等が挙げられる。)
・アシルオキシ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセトキシ、ベンゾイルオキシ等が挙げられる。)
・アシルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセチルアミノ、ベンゾイルアミノ等が挙げられる。)
・アルコキシカルボニルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニルアミノ等が挙げられる。)
・アリールオキシカルボニルアミノ基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルアミノ等が挙げられる。)
・スルホニルアミノ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノ等が挙げられる。)
・スルファモイル基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~12であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイル等が挙げられる。)
・カルバモイル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばカルバモイル、メチルカルバモイル、ジエチルカルバモイル、フェニルカルバモイル等が挙げられる。)
・アルキルチオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメチルチオ、エチルチオ等が挙げられる。)
・アリールチオ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルチオ等が挙げられる。)
・ヘテロ環チオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルチオ、2-ベンズイミゾリルチオ、2-ベンズオキサゾリルチオ、2-ベンズチアゾリルチオ等が挙げられる。)
・スルホニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメシル、トシル等が挙げられる。)
・スルフィニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルフィニル、ベンゼンスルフィニル等が挙げられる。)
・ウレイド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばウレイド、メチルウレイド、フェニルウレイド等が挙げられる。)
・リン酸アミド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばジエチルリン酸アミド、フェニルリン酸アミド等が挙げられる。)
・ヒドロキシ基、メルカプト基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、スルホ基、カルボキシル基、ニトロ基、トリフルオロメチル基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、複素環基(好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、具体的にはイミダゾリル、ピリジル、キノリル、フリル、チエニル、ピペリジル、モルホリノ、ベンズオキサゾリル、ベンズイミダゾリル、ベンズチアゾリル、カルバゾリル基、アゼピニル基等が挙げられる。)
・シリル基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリル、トリフェニルシリル等が挙げられる。)
・シリルオキシ基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリルオキシ、トリフェニルシリルオキシ等が挙げられる。)
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(A)186.2mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は78%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(B)203.1mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しジクロロメタンを加え抽出した。油層を回収し、減圧濃縮し得られた固体をジクロロメタンとメタノールを用いて再結晶した。化合物の同定は1H-NMRを用いて行い、化合物(4)であることを確認した。化合物(4)の単離収率は70%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(C)207.8mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。この生成物をシリカゲルカラムクロマトグラフィー(溶離液:ジクロロメタン)で精製した。化合物の同定は1H-NMRを用いて行い、化合物(5)であることを確認した。化合物(5)の単離収率は75%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(D)246.3mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(10)であることを確認した。化合物(10)の単離収率は80%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(E)313.6mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(12)であることを確認した。化合物(12)の単離収率は75%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(F)173.0mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(14)であることを確認した。化合物(12)の単離収率は65%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)807.6mg、化合物(G)528.0mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(16)であることを確認した。化合物(16)の単離収率は60%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(H)277.6mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(36)であることを確認した。化合物(36)の単離収率は80%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(I)294.4mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。さらにシリカゲルカラムクロマトグラフィー(溶離液:ジクロロメタン)で精製した。化合物の同定は1H-NMRを用いて行い、化合物(39)であることを確認した。化合物(39)の単離収率は70%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(A)186.2mg、及びエチレングリコール5mlをアルゴン雰囲気下、150℃で34時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は70%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mgに水を加えて10倍希釈した後、化合物(A)186.2mg、及びエチレングリコール50mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収しメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は60%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(A)186.2mg、及びジエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は60%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mgを計りとり、エバポレータで溶液を減圧留去した後、化合物(A)186.2mg、及びジエチレングリコール5mlを入れ、アルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は75%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(A)93.1mg、化合物(D)123.2mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。得られた固体の収量は102mgであった。HPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、(1)、(34)、(35)の生成割合は、それぞれ84.1%、15.2%、0.7%(ピーク面積の比率)であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)403.8mg、化合物(A)31.0mg、化合物(D)205.3mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。得られた固体の収量は110mgであった。HPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、(1)、(10)、(34)、(35)の生成割合は、それぞれ3.7%、52.2%、11.9%、32.2%(ピーク面積の比率)であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)807.6mg、化合物(A)124mg、化合物(I)98mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却した後、ジクロロメタンを加え抽出した。有機層を減圧濃縮し析出した固体を、シリカゲルクロマトグラフィー(溶離液:ジクロロメタン)を用いて原点不純物を除去した。精製後に得られた固体の収量は196mgであった。HPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、(1)、(37)、(38)、(39)の生成割合は、それぞれ17.9%、40.6%、31.8%、9.7%(ピーク面積の比率)であった。
硝酸イリジウムの黒色固体(イリジウム含有率53.48wt%)71.9mg、化合物(A)109.0mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。さらに、シリカゲルクロマトグラフィー(溶離液:ジクロロメタン)を用いて原点不純物を除去し、黄色固体を得た。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は93%であった。
硝酸イリジウムの黒色固体(イリジウム含有率54.12wt%)71.0mg、化合物(D)143.5mg、及びエチレングリコール5mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却しメタノールを加えた。析出した固体をろ過して回収し、メタノールで洗浄した。さらに、シリカゲルクロマトグラフィー(溶離液:ジクロロメタン)を用いて原点不純物を除去し、赤色固体を得た。化合物の同定は1H-NMRを用いて行い、化合物(10)であることを確認した。化合物(10)の単離収率は73%であった。
硝酸イリジウム水溶液(イリジウム含有率9.52wt%)807.6mg、化合物(A)248mg、化合物(I)196mg、及びエチレングリコール15mlをアルゴン雰囲気下、180℃で17時間加熱反応した。反応混合物を室温まで冷却した後、ジクロロメタンを加え抽出した。有機層を減圧濃縮し析出した固体を、シリカゲルクロマトグラフィー(溶離液:ジクロロメタン)を用いて原点不純物を除去した。精製後に得られた固体の収量は236mgであった。HPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、(1)、(37)、(38)、(39)の生成割合は、それぞれ17.3%、68.5%、8.4%、5.8%(ピーク面積の比率)であった。
実施例1の硝酸イリジウム水溶液の代わりに、従来のイリジウム原料であるトリス(2,4-ペンタンジオナト)イリジウム(III)を用いて同様に反応させた。しかし、化合物(1)は全く得られなかった。
実施例1の硝酸イリジウム水溶液の代わりに塩化イリジウム(III)n水和物を用いて反応させたが、塩素架橋ダイマーが得られ、化合物(1)は全く得られなかった。
実施例4の硝酸イリジウム水溶液の代わりに、従来のイリジウム原料であるトリス(2,4-ペンタンジオナト)イリジウム(III)を用いて同様に反応させた。しかし、化合物(10)は全く得られなかった。
実施例4の硝酸イリジウム水溶液の代わりに塩化イリジウム(III)n水和物を用いて反応させたが、塩素架橋ダイマーが得られ、化合物(10)は全く得られなかった。
実施例1で得られた化合物(1)をHPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、フェイシャル体とメリジオナル体の生成比が99.64:0.36(ピーク面積比)であった。
実施例4で得られた化合物(10)をHPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、フェイシャル体とメリジオナル体の生成比が99.57:0.43(ピーク面積比)であった。
実施例1で用いた硝酸イリジウム水溶液に替えて、硫酸イリジウム(IV)n水和物を用い、それ以外の方法は実施例1と同様にして化合物(1)を製造した。使用した硫酸イリジウム(IV)n水和物は、市販品(販売元:三津和化学工業株式会社)である。そして、得られた化合物(1)をHPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、フェイシャル体とメリジオナル体の生成比が99.97:0.03(ピーク面積比)であった。
実施例1の硝酸イリジウム水溶液の代わりに酢酸イリジウム(ChemPur GmbH 製)を用いる以外は、実施例1と同様に反応させた。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は75%であった。得られた化合物(1)をHPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、フェイシャル体とメリジオナル体の生成比が83.59:16.41(ピーク面積比)であった。
実施例4の硝酸イリジウム水溶液の代わりに酢酸イリジウム(ChemPur GmbH 製)を用いる以外は、実施例4と同様に反応させた。化合物の同定は1H-NMRを用いて行い、化合物(10)であることを確認した。化合物(10)の単離収率は75%であった。得られた化合物(10)をHPLC(島津製作所社製 Prominence、カラム:順相シリカゲル、移動相:THF(40%)とヘキサン(60%)の混合溶媒、検出波長:300nm)で分析した結果、フェイシャル体とメリジオナル体の生成比が99.24:0.76(ピーク面積比)であった。
Claims (11)
- イリジウム化合物からなる原料と、イリジウム-炭素結合を形成しうる芳香族複素環2座配位子と、を反応させてシクロメタル化イリジウム錯体を製造する方法において、
前記原料として強酸の共役塩基を配位子として有する非ハロゲン化イリジウムを反応させることを特徴とするシクロメタル化イリジウム錯体の製造方法。 - 非ハロゲン化イリジウムの配位子は、pKaが3以下の強酸の共役塩基である請求項1記載のシクロメタル化イリジウム錯体の製造方法。
- 非ハロゲン化イリジウムは、硝酸イリジウム又は硫酸イリジウムである請求項1又は請求項2記載のシクロメタル化イリジウム錯体の製造方法。
- 非ハロゲン化イリジウムは、固体状態である請求項1~請求項3のいずれかに記載のシクロメタル化イリジウム錯体の製造方法。
- 非ハロゲン化イリジウムは、溶媒に溶解又は分散している請求項1~請求項3のいずれかに記載のシクロメタル化イリジウム錯体の製造方法。
- 非ハロゲン化イリジウムを含む溶液のpHが0~3の範囲である請求項5記載のシクロメタル化イリジウム錯体の製造方法。
- シクロメタル化イリジウム錯体は、ビスシクロメタル化イリジウム錯体又はトリスシクロメタル化イリジウム錯体である請求項1~請求項6のいずれかに記載のシクロメタル化イリジウム錯体の製造方法。
- シクロメタル化イリジウム錯体として、ホモレプティックトリスシクロメタル化イリジウム錯体又はヘテロレプティックトリスシクロメタル化イリジウム錯体の少なくともいずれかを製造する請求項1~請求項7のいずれかに記載のシクロメタル化イリジウム錯体の製造方法。
- 強酸の共役塩基を配位子として有する非ハロゲン化イリジウムと、一般式(1)で表わされる芳香族複素環2座配位子とを反応させて、一般式(2)で表わされるシクロメタル化イリジウム錯体を製造する請求項1~請求項8のいずれかに記載の方法。
- 強酸の共役塩基を配位子として有する非ハロゲン化イリジウムと、一般式(1)で表わされる芳香族複素環2座配位子と、一般式(3)で表わされる芳香族複素環2座配位子とを反応させて、一般式(4)で表わされるシクロメタル化イリジウム錯体を製造する請求項1~請求項8に記載の方法。
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KR20180086483A (ko) | 2018-07-31 |
US10533027B2 (en) | 2020-01-14 |
JPWO2017122516A1 (ja) | 2018-11-08 |
CN108463465A (zh) | 2018-08-28 |
DE112016006231T5 (de) | 2018-10-18 |
TWI616450B (zh) | 2018-03-01 |
JP6651168B2 (ja) | 2020-02-19 |
TW201725211A (zh) | 2017-07-16 |
US20180362565A1 (en) | 2018-12-20 |
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