JP4662998B2 - 高発光効率の赤色リン光材料及びこれを含有している表示素子 - Google Patents
高発光効率の赤色リン光材料及びこれを含有している表示素子 Download PDFInfo
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- JP4662998B2 JP4662998B2 JP2007553028A JP2007553028A JP4662998B2 JP 4662998 B2 JP4662998 B2 JP 4662998B2 JP 2007553028 A JP2007553028 A JP 2007553028A JP 2007553028 A JP2007553028 A JP 2007553028A JP 4662998 B2 JP4662998 B2 JP 4662998B2
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- hydrogen
- red phosphorescent
- halogen
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- 239000000463 material Substances 0.000 title description 28
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000000126 substance Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 239000003446 ligand Substances 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 19
- -1 n -Butyl Chemical group 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- 150000002431 hydrogen Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 125000004450 alkenylene group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- KYPOHTVBFVELTG-UHFFFAOYSA-N but-2-enedinitrile Chemical group N#CC=CC#N KYPOHTVBFVELTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002019 doping agent Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 125000004076 pyridyl group Chemical group 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 7
- 229940093475 2-ethoxyethanol Drugs 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- VLRSADZEDXVUPG-UHFFFAOYSA-N 2-naphthalen-1-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CC2=CC=CC=C12 VLRSADZEDXVUPG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 5
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000011259 mixed solution Substances 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
- 238000005424 photoluminescence Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002504 iridium compounds Chemical class 0.000 description 3
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RBYUCFIZMNKDGX-UHFFFAOYSA-N 1,2-dihydroacenaphthylen-5-ylboronic acid Chemical compound C1CC2=CC=CC3=C2C1=CC=C3B(O)O RBYUCFIZMNKDGX-UHFFFAOYSA-N 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
- PZSISEFPCYMBDL-UHFFFAOYSA-N 2-bromo-3-methylpyridine Chemical compound CC1=CC=CN=C1Br PZSISEFPCYMBDL-UHFFFAOYSA-N 0.000 description 1
- JAUPUQRPBNDMDT-UHFFFAOYSA-N 2-chloropyridine-3-carbonitrile Chemical compound ClC1=NC=CC=C1C#N JAUPUQRPBNDMDT-UHFFFAOYSA-N 0.000 description 1
- SCXBFXGVOQYURB-UHFFFAOYSA-N 2-phenyl-1h-isoquinoline Chemical compound C1=CC2=CC=CC=C2CN1C1=CC=CC=C1 SCXBFXGVOQYURB-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- UUESRJFGZMCELZ-UHFFFAOYSA-K aluminum;2-methylquinoline-8-carboxylate;4-phenylphenolate Chemical compound [Al+3].C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC=C(C([O-])=O)C2=NC(C)=CC=C21.C1=CC=C(C([O-])=O)C2=NC(C)=CC=C21 UUESRJFGZMCELZ-UHFFFAOYSA-K 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-N aluminum;quinolin-8-ol Chemical compound [Al+3].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000005748 halopyridines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
-
- 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
- C09K2211/1011—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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Pyridine Compounds (AREA)
Description
(式中、 Lは下記のリガンドから選ばれ;
R1乃至R10は、互いに独立に水素、ハロゲンが置換もしくは無置換の直鎖もしくは分枝鎖のC1乃至C20アルキル基またはアルコキシ基、C5乃至C7シクロアルキル基、ハロゲンが置換もしくは無置換の芳香族基、ハロゲン基、アシル基、シアノ基、またはジシアノエチレン基であり、または、R5乃至R10は、互いに隣り合った炭素の置換基が炭素数2乃至10からなるアルキレンまたはアルケニレンで結合されて縮合環または多重縮合環を形成することができ、但し、前記縮合環または多重縮合環を形成しないときは、R4及びR5が、共に水素であるものは除く。)
(式中、R2、R4、R5、R8及びR9は、互いに独立に水素、メチル、エチル、n-プロピル、i-プロピル、n-ブチル、i-ブチル、t-ブチル、n-ペンチル、i-アミル、n-ヘキシル、n-ヘプチル、n-オクチル、2-エチルヘキシル、n-ノニル、トリフルオロメチル、ペンタフルオロエチル、シクロペンチル、シクロヘキシル、メトキシ、エトキシ、トリフルオロメトキシ、フェニル、2-メチルフェニル、4-メチルフェニル、2-フルオロフェニル、4-フルオロフェニル、1-ナフチル、2-ナフチル、フルオロ、アセチル基、ベンゾイル、ホルミル、ピバロイル、またはシアノ基であり、但し、R4及びR5が共に水素であるものは除く。)
(前記の化学式8乃至化学式12の化合物のR2、R4及びR5は、互いに独立に水素、メチル、エチル、n-プロピル、i-プロピル、n-ブチル、i-ブチル、t-ブチル、n-ペンチル、i-アミル、n-ヘキシル、n-ヘプチル、n-オクチル、2-エチルヘキシル、n-ノニル、トリフルオロメチル、ペンタフルオロエチル、シクロペンチル、シクロヘキシル、メトキシ、エトキシ、トリフルオロメトキシ、フェニル、2-メチルフェニル、4-メチルフェニル、2-フルオロフェニル、4-フルオロフェニル、1-ナフチル、2-ナフチル、フルオロ、アセチル基、ベンゾイル、ホルミル、ピバロイル、またはシアノ基である。)
R06の製造
1-ナフタレンボロン酸(1-naphthalene boronic acid)4.7g(27.3mmol)、2-クロロ-3-シアノピリジン(2-chloro-3-cyanopyridine)3.6g(26.0mmol)、及び Pd(PPh3)4(tetrakis(triphenylphosphine)palladium)1.5g(1.3mmol)をトルエン−エタノール混合溶媒(5:5)100mLに溶かした後、2M炭酸ナトリウム水溶液40mLを添加して16時間還流させた。反応を停止させた後、常温まで冷却させ酢酸エチルで抽出してクロロホルムで再結晶し、白色固体のR06の主リガンド4.5g(19.5mmol)を得た。
1H NMR(200MHz, CDCl3): δ7.3-7.4(m, 4H), 7.6-7.7(m, 3H), 8.0-8.2(m, 2H), 9.1(d, 1H)
前記段階で製造されたリガンドR06 3.0g(13.0mmol)と塩化イリジウム(III)1.2g(5.9mmol)を2-エトキシエタノール45mLに溶かして、12時間還流させた。生成された固体を濾過して、水で洗った後、塩化メチレンで抽出し、トルエン混合溶液で再結晶して、相応する赤色結晶のμ−ジクロロジイリジウム中間体である[R06]2Ir2Cl2[R06]2を1.7g収得した。
1H NMR(200MHz, CDCl3): δ2.1(s, 6H), 5.5-5.6(s, 1H), 7.3-8.5(m, 18H)
MS/FAB: 750(測定値), 749.84(計算値)
リガンドR16の製造
5-アセナフタレンボロン酸(5-acenaphthene boronic acid)3.28g(16.6mmol)、2-ブロモ-3-メチルピリジン(2-bromo-3-methylpyridine)2.59g(15.0mmol)、及びPd(PPh3)40.52g(0.45mmol)をトルエン−エタノール混合溶媒(5:5) 100mLに溶かした後、2M炭酸ナトリウム水溶液30mLを添加し16時間還流させた。反応を停止させた後、室温まで冷却させ酢酸エチルで抽出し、クロロホルムで再結晶して白色固体のR16を2.1g(8.1mmol)得た。
1H NMR(200MHz, CDCl3): δ2.3(s, 3H), 3.4(t, 4H), 6.9(m, 1H), 7.1(d, 1H), 7.2(d, 1H), 7.3(m, 1H), 7.4-7.5(m, 2H), 8.1(d, 2H), 8.5(d, 1H)
前記段階で製造されたリガンドR16を2.0g(7.7mmol)用いて実施例1と同一の方法で表題化合物である赤色リン光化合物の[R16]2[acac]Ir0.41g(0.53mmol、収率15%)を得た。
1H NMR(200MHz, CDCl3): δ2.1(s, 6H), 2.35(s, 6H), 3.4(t, 8H), 5.5-5.6(s, 1H), 7.1-8.4(m, 14H)
MS/FAB: 781(測定値), 779.95(計算値)
リガンドR18の製造
1-ナフタレンボロン酸4.28g(24.9mmol)、2,3-ジクロロピリジン(2,3-dichloropyridine)1.84g(12.45mmol)、及びPd(PPh3)40.71g(0.62mmol)をトルエン−エタノール混合溶媒(5:5)100mLに溶かした後、2M炭酸ナトリウム水溶液60mLを添加し、48時間還流させた。反応を停止させた後、常温まで冷却させ酢酸エチルで抽出してクロロホルムで再結晶して白色固体のR18を3.0g(9.1mmol)得た。
1H NMR(200MHz, CDCl3): δ7.05(m, 1H), 7.3-7.7(m, 14H), 8.1(d, 2H), 8.5-8.6(m, 2H)
前記段階で得られたリガンドR18を3.0g(9.1mmol)用いて、実施例1と同一の方法で表題化合物である赤色リン光化合物の[R18]2[acac]Ir1.26g(1.32 mmol、収率41%)を得た。
1H NMR(200MHz, CDCl3): δ2.1(s, 6H), 5.5-5.6(s, 1H), 7.3-8.5(m, 32H)
MS/FAB: 953(測定値), 952.14(計算値)
リガンドR19の製造
フルオランテン(fluoranthene)を1-臭素化して製造された1-フルオランテンボロン酸(1-fluoranthene boronic acid)2.36g(9.59mmol)、2-ブロモピリジン1.52g(9.62mmol)、及びPd(PPh3)40.27g(0.24mmol)をトルエン−エタノール混合溶媒(5:5)80mLに溶かした後、2M炭酸ナトリウム水溶液60mLを添加し、24時間還流させた。反応を停止させた後、常温まで冷却させ酢酸エチルで抽出してクロロホルムで再結晶して白色固体のリガンドR19を2.2g(7.85mmol)得た。
1H NMR(200MHz, CDCl3): δ6.95(q, 1H), 7.25(s, 4H), 7.45-7.55(m, 2H), 7.8(d, 1H), 7.9(d, 1H), 8.0(d, 1H), 8.3(d, 1H), 8.55(d, 1H)
前記段階で製造されたリガンドR19 2.2g(7.85mmol)を用いて実施例1と同一の方法で表題化合物の[R19]2[acac]Ir1.5g(1.77mmol、収率49%)を得た。
1H NMR(200MHz, CDCl3): δ2.1(s, 6H), 5.5-5.6(s, 1H), 7.0-7.15(m, 2H), 7.3-7.4(s, 8H), 7.5-8.5(m, 14H)
MS/FAB: 848(測定値), 847.98(計算値)
[2-(1-ナフチル)ピリジン]2[acac]Irの製造
1-ナフタレンボロン酸(naphthalene boronic acid)1.90g(11.0mmol)、2-ブロモピリジン(2-bromopyridine)1.58g(10.0mmol)、及びPd(PPh3)40.64g (0.55mmol)をトルエン−エタノール混合溶媒(5:5)100mLに溶かした後、2M炭酸ナトリウム水溶液30mLとピリジン1mLを添加し1日間還流させた。反応を停止させた後、常温まで冷却し酢酸エチルで抽出してクロロホルムで再結晶して白色固体の表題化合物(R1乃至R10が全て水素)であるリガンド1.74g(8.5mmol)を収得した。
1H NMR(200MHz, CDCl3): δ2.1(s, 6H), 5.5-5.6(s, 1H), 6.9-7.9(m, 20H)
MS/FAB: 702(測定値), 701.83(計算値)
本発明による赤色リン光化合物と比較例1から製造した光発光材料を光発光ドーパントとして使用してOLED素子を製作した。
材料別に合成収率が高い錯体は、10-6torr下において真空昇華精製してOLED光発光層のドーパントで使用し、合成収率が低い材料の場合は、光発光ピークのみを確認した。この際、光発光ピークは10-4M以下の濃度の塩化メチレン溶液を製造して測定した。あらゆる材料の光発光の測定時、励起(excitation)波長は250nmで行った。
[産業上利用可能性]
1−有機EL用ガラス 2−透明電極ITO薄膜
3−正孔伝達層 4−光発光層
5−正孔ブロッキング層 6−電子伝達層
7−電子注入層 8−負極
Claims (6)
- 下記化学式1で表される赤色リン光化合物。
<化学式1>
- 化学式1の化合物は、R1乃至R10が互いに独立に水素、直鎖もしくは分枝鎖のC1乃至C10アルキル基またはアルコキシ基、C5乃至C7シクロアルキル、ハロゲン基、アシル基、シアノ基、C5乃至C7シクロアルキル基、またはハロゲンが置換もしくは無置換の芳香族基であり、但し、R4及びR5が共に水素であるものは除かれることを特徴とする請求項1に記載の赤色リン光化合物。
- 下記の化学式3乃至化学式7で表される請求項1に記載の赤色リン光化合物。
<化学式3>
- 下記の化学式2、および化学式8乃至化学式12から選ばれる請求項1に記載の赤色リン光化合物。
<化学式2>
- 下記化学式の化合物から選ばれる請求項4に記載の赤色リン光化合物。
- 請求項1乃至5のいずれかに記載の赤色リン光化合物を含む表示素子。
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US8399665B2 (en) | 2009-10-07 | 2013-03-19 | Semiconductor Energy Laboratory Co., Ltd. | Organometallic complex, and light-emitting element, light-emitting device, electronic device and electronic device using the organometallic complex |
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