WO2006112582A1 - Deuterated organic electroluminescent material, preparation method thereof and organic light emitting diode using the same - Google Patents
Deuterated organic electroluminescent material, preparation method thereof and organic light emitting diode using the same Download PDFInfo
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- WO2006112582A1 WO2006112582A1 PCT/KR2005/003840 KR2005003840W WO2006112582A1 WO 2006112582 A1 WO2006112582 A1 WO 2006112582A1 KR 2005003840 W KR2005003840 W KR 2005003840W WO 2006112582 A1 WO2006112582 A1 WO 2006112582A1
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- WIPO (PCT)
- Prior art keywords
- compound
- formula
- group
- deuterium
- light emitting
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 78
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 26
- 229910052805 deuterium Inorganic materials 0.000 claims description 26
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- -1 amine compound Chemical class 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- 229910052757 nitrogen Inorganic materials 0.000 claims 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- 239000010410 layer Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane 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-K 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 235000021286 stilbenes Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-DYVTXVBDSA-N (2,3,4,5,6-pentadeuteriophenyl)-phenylmethanone Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-DYVTXVBDSA-N 0.000 description 2
- UJOBWOGCFQCDNV-MKANTAFVSA-N 1,2-dideuterio-9h-carbazole Chemical compound C1=CC=C2C3=CC=C([2H])C([2H])=C3NC2=C1 UJOBWOGCFQCDNV-MKANTAFVSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- LNZNQIKMFXUTNV-ZWFZLLPRSA-N 4-(9H-carbazol-1-yl)-2,3-dideuteriobenzaldehyde Chemical compound C1(=CC=CC=2C3=CC=CC=C3NC1=2)C1=C(C(=C(C=O)C=C1)[2H])[2H] LNZNQIKMFXUTNV-ZWFZLLPRSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- MNRIYVANSCJUHM-UHFFFAOYSA-N 1-(diethoxyphosphorylmethyl)-2-phenylbenzene Chemical group CCOP(=O)(OCC)CC1=CC=CC=C1C1=CC=CC=C1 MNRIYVANSCJUHM-UHFFFAOYSA-N 0.000 description 1
- DRCOGQJUVZRNSQ-UHFFFAOYSA-N 1-(diethoxyphosphorylmethyl)-4-[4-(diethoxyphosphorylmethyl)phenyl]benzene Chemical group C1=CC(CP(=O)(OCC)OCC)=CC=C1C1=CC=C(CP(=O)(OCC)OCC)C=C1 DRCOGQJUVZRNSQ-UHFFFAOYSA-N 0.000 description 1
- CHWZRUDKIJOVOX-UHFFFAOYSA-N 1-[4-[2-[4-(9h-carbazol-1-yl)phenyl]ethenyl]phenyl]-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C1=CC=C(C=C1)C=CC=1C=CC(=CC=1)C=1C3=C(C4=CC=CC=C4N3)C=CC=1)=CC=C2 CHWZRUDKIJOVOX-UHFFFAOYSA-N 0.000 description 1
- JEHMPNUQSJNJDL-OWOJBTEDSA-N 1-bromo-4-[(e)-2-(4-bromophenyl)ethenyl]benzene Chemical compound C1=CC(Br)=CC=C1\C=C\C1=CC=C(Br)C=C1 JEHMPNUQSJNJDL-OWOJBTEDSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JQUYTOOXCNJPTD-ZMERNRJISA-N 9-[4-[2-(4-carbazol-9-ylphenyl)ethenyl]-2,3,5,6-tetradeuteriophenyl]carbazole Chemical class C1=CC=CC=2C3=CC=CC=C3N(C1=2)C1=C(C(=C(C(=C1[2H])[2H])C=CC1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC=CC1=2)[2H])[2H] JQUYTOOXCNJPTD-ZMERNRJISA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005055 short column chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 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
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/327—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae characterised by animals and plants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/58—Naphthylamines; N-substituted derivatives thereof
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B3/00—Engineering works in connection with control or use of streams, rivers, coasts, or other marine sites; Sealings or joints for engineering works in general
- E02B3/04—Structures or apparatus for, or methods of, protecting banks, coasts, or harbours
- E02B3/043—Artificial seaweed
-
- 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
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Definitions
- the present invention relates to a deuterated organic electroluminescent material, a preparation method thereof and an organic light emitting diode using the same.
- U.S. Patent No. 6,699,599 discloses a phosphorescent material that hydrogen atoms of Ir(ppy) are partially or entirely substituted with deuterium.
- the substitution of hydrogen of a compound with the deuterium makes exciton formed easily, resulting in enhancing light emitting efficiency.
- the reason is that the bond strength between carbon and deuterium is stronger than that between carbon and hydrogen, and thus, if a substitution with deuterium is performed, the bond length between carbon and deuterium is shortened, and a van der Waals' force becomes smaller, so that higher light emitting efficiency can be achieved.
- a deuterated organic electroluminescent material a preparation method thereof and an organic light emitting diode using the same.
- the organic light emitting diode using the deuterated organic electroluminescent material has remarkably improved emitting efficiency, brightness, power efficiency, thermal stability and the like.
- the compound according to the present invention can be applied to an emitting layer, a hole transport layer and/or an electron transport layer of an organic light emitting diode.
- the compound according to the present invention is a low molecular weight chromophore compound, and thus, if it is applied to a light emitting diode, a blue light can take place at a low voltage.
- the compound according to the present invention is an organic matter having a conjugated double bond, and thus, various colors can be embodied by employing another emitting material as a dopant.
- the compound according to the present invention is super in its brightness and light emitting efficiency.
- Fig. 1 shows efficiency test results of diodes comprising Compound A and
- Fig. 2 shows an efficiency test results of diodes comprising Compound C and
- Fig. 3 shows an efficiency test results of diodes comprising Compound E and
- an organic electroluminescent material of the present invention has a structure represented by Formula 1 as follows: [16] Formula 1
- Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R, CH and SiR , or may be directly connected to each other without a linker; and
- R and R' are independently selected from the group consisting of hydrogen, deuterium, CN, F and CH ;
- the compound of Formula 1 has one or more deuterium within a molecule.
- Formula 4
- deuterium may be introduced in a manner that a compound to which deuterium is introduced is added to an aqueous solution in which boron trifluoride is dissolved in heavy water, and the resulting solution is then stirred for at least 48 hours.
- the deuterium may be introduced in a manner of obtaining un-deuterated compound of Formula 1 from an un-deuterated starting material, followed by deuterating un- deuterated compound of Formula 1, or in a manner of deuterating the starting material, followed by obtaining the deuterated compound of Formula 1 using the deuterated starting material.
- the present invention also relates to a light emitting diode using the compound of
- the compound of Formula 1 is applied between an anode for injecting a hole comprising indium tin oxide (ITO) having a high work function and a cathode for injecting an electron comprising a metal such as aluminum, lithium fluoride/aluminum, copper, silver, calcium, gold, magnesium or the like, or alloys thereof having various work functions.
- ITO indium tin oxide
- cathode for injecting an electron comprising a metal such as aluminum, lithium fluoride/aluminum, copper, silver, calcium, gold, magnesium or the like, or alloys thereof having various work functions.
- the compound of Formula 1 can also be applied to an emitting layer, a hole transport layer and/or an electron transport layer of a light emitting diode.
- the structures of the compounds prepared in examples were determined by H-NMR, elemental analysis, mass spectrometry and the like. UV and PL spectra were measured in a solution of a compound in dichloromethane. Organic light emitting diodes were prepared so as to evaluate emitting properties thereof.
- Table 3 shows brightness and current efficiency of Compound C
- Table 4 shows brightness and current efficiency of Compound D. As shown in Tables 3 and 4, it can be confirmed that the brightness and current efficiency of Compound C of Example 2 are remarkably superior to those of Compound D.
- FIG. 2 shows an illustration of the current efficiency data among the results shown in Tables 3 and 4.
- Example 3 Preparation of 4,4'-bis(l,2'-dinaphthylamino)stilbene-d4 (Compound E) [72] After 10 g (0.069 mole) of 2-naphthol, 10 g (0.070 mole) of 1-naphthylamine (available from Aldrich Co.) and 0.8 g of phosphoric acid were added to a 100 ml flask, and the resulting mixture was refluxed with stirring using 1,2-dichlorobenzene as a solvent for 12 hours. The completion of the reaction was checked by TLC. After the reaction was completed, the reaction mixture was purified by a column chromatography to obtain 14 g (0.052 mole) of l,2'-dinaphthylamine (yield: 75%).
- the reaction solution was poured onto a thin silica pad so as to perform a short column chromatography, and then washed with dichloromethane.
- the residue was distilled under reduced pressure so as to remove solvent and then dried.
- the obtained residue was added into a 100 ml flask. After 50 ml of heavy water was added into the flask, boron trifluoride gas was introduced into the reaction mixture for 15 minutes, and then the resulting mixture was stirred at an ambient temperature for 48 hours.
- the reaction mixture was poured into 200 ml of distilled water and sodium hydroxide was added until pH of the solution became 7 so as to neutralize.
- the reaction mixture was then filtered and then the filtrate was dried.
- the dried residue was dissolved in toluene and purified by a silica gel chromatography, to obtain 1.64 g (2.29 mmol) of
- Fig. 3 shows an illustration of the current efficiency data among the results shown in Tables 5 and 6.
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Abstract
Provided are a deuterated organic electroluminescent material, a preparation method thereof and an organic light emitting diode using the same. The organic light emitting diode using the deuterated organic electroluminescent material of the present invention has remarkably improved emitting efficiency, brightness, power efficiency, thermal stability and the like.
Description
Description
DEUTERATED ORGANIC ELECTROLUMINESCENT MATERIAL, PREPARATION METHOD THEREOF AND
ORGANIC LIGHT EMITTING DIODE USING THE SAME
Technical Field
[1] The present invention relates to a deuterated organic electroluminescent material, a preparation method thereof and an organic light emitting diode using the same.
Background Art
[2] U.S. Patent No. 6,699,599 discloses a phosphorescent material that hydrogen atoms of Ir(ppy) are partially or entirely substituted with deuterium. In general, the substitution of hydrogen of a compound with the deuterium makes exciton formed easily, resulting in enhancing light emitting efficiency. The reason is that the bond strength between carbon and deuterium is stronger than that between carbon and hydrogen, and thus, if a substitution with deuterium is performed, the bond length between carbon and deuterium is shortened, and a van der Waals' force becomes smaller, so that higher light emitting efficiency can be achieved.
[3] However, U.S. Patent No. 6,699,599 does not present in numerical values of the extent to which the efficiency has been improved, where hydrogen(s) of the Ir(ppy) is substituted with deuterium, compared with the case that hydrogen is not substituted. Rather, it can be only presumed that the efficiency has been slightly improved. Disclosure of Invention
Technical Problem
[4] Therefore, it is an object of the present invention to provide a deuterated low molecular weight organic electroluminescent material, which can be applied to an emitting layer, a hole transport layer and/or an electron transport layer of an organic light emitting diode, a preparation method thereof and an organic light emitting diode using the same.
[5] It is another object of the present invention to provide a d euterated organic electroluminescent material, which can remarkably enhance emitting efficiency, thermal stability or the like of an emitting diode compared with a conventional organic electroluminescent material, a preparation method thereof and an organic light emitting diode using the same.
[6] It is still another object of the present invention to provide deuterated organic electroluminescent material, capable of being operated at a low voltage, expressing various colors and having a fast response, a preparation method thereof and an organic light emitting diode using the same.
Technical Solution
[7] To achieve the above and other objects of the invention, there is provided a compound having a structure of a stilbene or a biphenyl ring substituted with a hetero- aromatic ring selected from the group consisting of a substituted or unsubstituted carbazole, aryl, aromatic amine, aliphatic amine, phenoxazine and phenothiazine, and having more than one or more deuterium within the compound.
Advantageous Effects
[8] According to the present invention, a deuterated organic electroluminescent material, a preparation method thereof and an organic light emitting diode using the same. The organic light emitting diode using the deuterated organic electroluminescent material has remarkably improved emitting efficiency, brightness, power efficiency, thermal stability and the like.
[9] Accordingly, the compound according to the present invention can be applied to an emitting layer, a hole transport layer and/or an electron transport layer of an organic light emitting diode.
[10] The compound according to the present invention is a low molecular weight chromophore compound, and thus, if it is applied to a light emitting diode, a blue light can take place at a low voltage. Also, the compound according to the present invention is an organic matter having a conjugated double bond, and thus, various colors can be embodied by employing another emitting material as a dopant. Furthermore, the compound according to the present invention is super in its brightness and light emitting efficiency.
Description of Drawings
[11] Fig. 1 shows efficiency test results of diodes comprising Compound A and
Compound B ( H : Compound A; and • : Compound B);
[12] Fig. 2 shows an efficiency test results of diodes comprising Compound C and
Compound D ( B : Compound C; and • : Compound D); and
[13] Fig. 3 shows an efficiency test results of diodes comprising Compound E and
Compound F ( B : Compound E; and • : Compound F).
Mode for Invention
[14] In an aspect of the present invention, there is provided a compound having a structure of a stilbene or a biphenyl ring substituted with a hetaro-aromatic ring selected from the group consisting of a substituted or unsubstituted carbazole, aryl, aromatic amine, aliphatic amine, phenoxazine and phenothiazine, and having more than one or more deuterium within the compound.
[15] Therefore, an organic electroluminescent material of the present invention has a structure represented by Formula 1 as follows:
[16] Formula 1
[17]
[ 18] wherein m and n represent 0 or 1 , respectively;
[19] B is N in the case of n=0 ;
[20] A is carbon and B is CH in the case of n=l ;
[21] Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R, CH and SiR , or may be directly connected to each other without a linker; and
[22] R and R' are independently selected from the group consisting of hydrogen, deuterium, CN, F and CH ;
[23] provided that the compound of Formula 1 has one or more deuterium within a molecule.
[24] The compound of Formula 1, in which m=l, can be prepared by reacting a secondary amine compound represented by Formula 2 with a stilbene compound represented by Formula 3 via Ullmann reaction or C-N bonding reaction using a palladium catalyst.
[25] Formula 2
[26]
Ar- NH - Ar1
[27] Formula 3
[28]
[29] The compound of Formula 1, in which m=l, can also be obtained by reacting the compound of Formula 2 with a benzaldehyde compound represented by Formula 4 to obtain a compound of Formula 5, followed by coupling the compound of Formula 5 with each other.
[30] Formula 4
[31]
[32] Formula 5
[33]
[34] Meanwhile, the compound of Formula 1, in which n=0, can be obtained by converting a biphenyl compound represented by Formula 6 into a phosphonate compound so as to activate, followed by reacting the activated phosphonate compound with benzophenone.
[35] Formula 6
[36]
W \-/ x
[37] In Formulas 2 to 6, the Ar, Ar', R and R' are the same as defined for the compound of Formula 1 ; and X and Y are independently a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
[38] In preparing the compound of Formula 1 according to the present invention, deuterium may be introduced in a manner that a compound to which deuterium is introduced is added to an aqueous solution in which boron trifluoride is dissolved in heavy water, and the resulting solution is then stirred for at least 48 hours. At this time, the deuterium may be introduced in a manner of obtaining un-deuterated compound of Formula 1 from an un-deuterated starting material, followed by deuterating un- deuterated compound of Formula 1, or in a manner of deuterating the starting material, followed by obtaining the deuterated compound of Formula 1 using the deuterated starting material.
[39] The present invention also relates to a light emitting diode using the compound of
Formula 1. The compound of Formula 1 according to the present invention is applied between an anode for injecting a hole comprising indium tin oxide (ITO) having a high work function and a cathode for injecting an electron comprising a metal such as aluminum, lithium fluoride/aluminum, copper, silver, calcium, gold, magnesium or the
like, or alloys thereof having various work functions. The compound of Formula 1 can also be applied to an emitting layer, a hole transport layer and/or an electron transport layer of a light emitting diode.
[40] EXAMPLES
[41] Hereinafter, the present invention will now be described in detail with reference to the following examples. However, such examples are exemplary for the present invention, and accordingly, the scope of the present invention will not be limited thereto.
[42] In the present invention, the structures of the compounds prepared in examples were determined by H-NMR, elemental analysis, mass spectrometry and the like. UV and PL spectra were measured in a solution of a compound in dichloromethane. Organic light emitting diodes were prepared so as to evaluate emitting properties thereof.
[43] Example 1 : Preparation of Deuterated 4,4'-di(9-carbazolyl)stilbene-d4 (Compound
A)
[44] After 50 ml of heavy water was put in a 100 ml flask, 12 g (0.07 mole) of carbazole was added thereinto, and boron trifluoride gas was then injected for 15 minutes while stirring, and the resulting solution was stirred at an ambient temperature for 48 hours. After, the reaction mixture was poured into 200 ml of distilled water, sodium hydroxide was added thereto so as to neutralize until pH of the solution reached 7. The reaction mixture was then filtered and the filtrate was dried. The dried residue was dissolved in toluene and purified using a silica gel column chromatography, to obtain 10.8 g (0.064 mole) of carbazole-d2 (yield: 89%).
[45] 1O g (60 mmol) of the carbazole-d2 and 7.45 g (60 mmol) of 4-fluoro benzaldehyde
(available from Aldrich Co.) were put into a 100 ml flask. After 16.5 g of potassium carbonate was added into the flask, the reaction mixture was refluxed with stirring using N,N-dimethylformamide as a solvent for 4 hours. The completion of the reaction was confirmed by thin layer chromatography (TLC). After completion of the reaction, the reaction mixture was purified by a column chromatography to obtain 14 g (0.051 mole) of 4-carbazolyl benzaldehyde-d2 (yield: 87%).
[46] After 5 g (0.0182 mole) of 4-carbazolyl benzaldehyde-d2 was put into a flask and dissolved in dried tetrahydrofuran, 3.0 g (0.0455 mole) of zinc powder was added thereto. Titanium tetrachloride was then gradually added to the reaction mixture for 30 minutes. After the addition of the titanium tetrachloride was completed, the reaction mixture was refluxed with stirring for 6 hours. The product was purified by a column chromatography and recrystallized from toluene to obtain 3.7 g (0.0071 mole) of the desired compound (Compound A). The yield of the final product was 78.5 %, and the produce has a very stable form.
[47] 1H-NMR (CDCl , 300MHz) δ (ppm) 8.16(d), 7.8(d), 7.6(d), 7.5-7.4(m) and 7.3(t)
[48] In order to compare with the emitting properties of the compound obtained in Example 1, 4,4'-dicarbazolylstilbene (Compound B) was prepared. Using Compound B and the compound prepared in Example 1, respectively, organic light emitting diodes were constructed as described below, and their light emitting properties were evaluated.
[49] ITO/m-MTDATA(600 nm)/NPB(200 nm)/Compound A(300 nm)/Alq3(250 nm) / LiF(IO nm)/Al [50] ITO/m-MTDATA(600 nm)/NPB(200 nm)/Compound B(300 nm)/Alq3(250 nm) / LiF(IO nm)/Al [51] Table 1 shows brightness and current efficiency of Compound A, and Table 2 shows brightness and current efficiency of Compound B. As shown in Tables 1 and 2, it can be confirmed that the brightness and current efficiency of Compound A according to Example 1 are remarkably superior to those of Compound B.
[52] Table 1 [53]
[54] [55]
[56] The efficiency depending on the current among the above results was illustrated in Figure 1. [57] Example 2: Preparation of 4,4'-bis(2,2'-diphenylethen-l-yl)biphenyl-dlO
(Compound C)
[58] After 18 g (0.21 mole) of benzene-d6, 20 g (0.14 mole) of benzoyl chloride and 6.8 g (0.05 mole) of aluminum trichloride were put into a 100 ml flask, the resulting mixture was refluxed for 6 hours. The reaction mixture then poured in 100 ml of water and then extracted with toluene. Organic layer was purified by silica gel chromatography, to give 24 g (0.128 mole) of benzophenone-d5 with an yield of 90%.
[59] 20 g (0.057 mole) of 4,4'-bromomethylbiphenyl and 37 ml (0.22 mole) of tri- ethylphosphite were added to a 100 ml flask, and the resulting mixture was refluxed for two hours. The reaction mixture was cooled down to room temperature, and stirred for two more hours after adding 50 ml of hexane thereto. The reaction mixture was then to obtain 21 g (0.0497 mole) of 4,4'-bis(diethoxyphosphorylmethyl)biphenyl with an yield of 87%.
[60] After 2.4 g (0.013 mole) of benzophenone-d5 and 2.17 g (0.05 mole) of 4,4'-bis
(diethoxyphosphorylmethyl)biphenyl were added to a 100 ml flask, anhydrous tetrahydrofuran was further added, and then, 0.37 g (0.015 mole) of sodium hydride was added. The reaction mixture was then refluxed for 12 hours. After the reaction solution was poured into methanol, the generated precipitate was filtered off, and the filtrate was concentrated. The concentrate was purified by a silica gel chromatography to obtain 1.1 g (0.021 mole) of 4,4'-bis(2,2-diphenyl- ethen-l-yl)biphenyl-dlθ. The final product was obtained with an yield of 41% and is in a very stabilized form.
[61] 1H-NMR(CDCl 3 , 300MH z) δ (ppm) 7.35-7.32(m), 7.26(s), 7.25-7.2 (m), 7.4(d),
6.98(s)
[62] 4,4'-Bis(2,2-diphenyl-ethen-l-yl)biphenyl (Compound D) was synthesized, in order to compare its emitting properties with those of the deuterated compound (Compound C) prepared in Example 2, organic light emitting diodes were constructed using Compounds C and D as emitting layers, respectively, as described below. Then, emitting properties of such emitting diodes were evaluated.
[63] ITO/m-MTDATA(450 nm)/NPB(150 nm)/Compound C(300 nm)/Alq3(250 nm) /
LiF(IO nm)/Al
[64] ITO/m-MTDATA(450 nm)/NPB(150 nm)/Compound D(300 nm)/Alq3(250 nm)/
LiF(IO nm)/Al
[65] Table 3 shows brightness and current efficiency of Compound C, and Table 4 shows brightness and current efficiency of Compound D. As shown in Tables 3 and 4, it can be confirmed that the brightness and current efficiency of Compound C of Example 2 are remarkably superior to those of Compound D.
[66] Table 3
[68] Table 4 [69]
[70] Fig. 2 shows an illustration of the current efficiency data among the results shown in Tables 3 and 4.
[71] Example 3: Preparation of 4,4'-bis(l,2'-dinaphthylamino)stilbene-d4 (Compound E) [72] After 10 g (0.069 mole) of 2-naphthol, 10 g (0.070 mole) of 1-naphthylamine (available from Aldrich Co.) and 0.8 g of phosphoric acid were added to a 100 ml flask, and the resulting mixture was refluxed with stirring using 1,2-dichlorobenzene as a solvent for 12 hours. The completion of the reaction was checked by TLC. After the reaction was completed, the reaction mixture was purified by a column chromatography to obtain 14 g (0.052 mole) of l,2'-dinaphthylamine (yield: 75%).
[73] 1 g (2.96 mmol) of 4,4'-dibromostilbene and 1.8 g (6.79 mmol) of l,2'-dinaphthylamine were dissolved in 20 ml of toluene. After 0.14 g (0.15 mmol) of tris(dibenzylideneacetone)dipalladium was introduced into the resulting mixture under nitrogen atmosphere, 1.1 g (11.4 mmol) of NaOBu' was added thereto. 0.3 g (1.48 mmol) of (t-Bu) P was further added into the reaction mixture, which was then stirred for 12 hours. After confirming completion of the reaction by TLC, the temperature of the reaction mixture was cooled down to an ambient temperature. The reaction solution was poured onto a thin silica pad so as to perform a short column chromatography, and then washed with dichloromethane. The residue was distilled under reduced pressure
so as to remove solvent and then dried. The obtained residue was added into a 100 ml flask. After 50 ml of heavy water was added into the flask, boron trifluoride gas was introduced into the reaction mixture for 15 minutes, and then the resulting mixture was stirred at an ambient temperature for 48 hours. The reaction mixture was poured into 200 ml of distilled water and sodium hydroxide was added until pH of the solution became 7 so as to neutralize. The reaction mixture was then filtered and then the filtrate was dried. The dried residue was dissolved in toluene and purified by a silica gel chromatography, to obtain 1.64 g (2.29 mmol) of
4,4'-bis(l,2'-dinaphthylamino)stilbene-d4 (Compound E). The final product was obtained with an yield of 78% and is in a very stabilized form.
[74] 1H-NMR(CDCl3 , 300MHz) δ (ppm) 7.92(q), 7.8(d), 7.67-7.75(m), 7.4-7.53(m), 7.23-7.38(m), 7.02(d), 6.9(s) [75] 4,4'-bis(l,2'-dinaphthylamino)stilbene (Compound F) was prepared, and in order to compare its emitting properties with those of the deuterated compound (Compound E) prepared in Example 3, organic light emitting diodes were constructed using Compounds E and F as a dopant of each emitting layer, respectively, as described below. Their emitting properties were evaluated.
[76] ITO/m-MTDATA(450 nm)/NPB(150 nm)/DPVBi(275 nm)+Compound E(25 nm) / Alq3(250 nm)/LiF(10 nm)/Al [77] ITO/m-MTDATA(450 nm)/NPB(150 nm)/DPVBi(275 nm)+Compound F(25 nm) / Alq3(250 nm)/LiF(10 nm)/Al [78] Table 5 shows brightness and current efficiency of the Compound E, and Table 6 shows brightness and current efficiency of the Compound F. As shown in Tables 5 and 6, it can be confirmed that the brightness and current efficiency of the Compound E of Example 3 of the present invention are remarkably superior to those of the Compound F, and its color purity has also been improved.
[79] Table 5 [80]
[81] Table 6
[82]
[83] Fig. 3 shows an illustration of the current efficiency data among the results shown in Tables 5 and 6. [84] As described above, the deuterated compound according to the present invention exhibits similar light emitting properties, with remarkably superior brightness and current efficiency, compared with the corresponding un-deuterated compound.
[85] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover such modifications and variations of the invention provided that they come within the scope of the appended claims and their equivalents.
Claims
[ 1 ] A deuterated compound represented by the following Formula 1 :
Formula 1
B represents a nitrogen atom in case of n=0; A represents a carbon atom and B represents CH in case of n=l ;
Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R,
CH and SiR , or may be directly connected to each other without a linker; and
R and R' are independently selected from the group consisting of hydrogen, deuterium, CN, F and CH ; provided that the compound of Formula 1 essentially has one or more deuterium within a molecule.
[2] The compound according to claim 1, wherein the Ar and Ar' are connected to each other so as to form a carbazole ring.
[3] The compound according to claim 1, wherein m is 1 and n is 0, and the Ar and Ar' are connected to each other so as to form a carbazole ring.
[4] The compound according to claim 1, wherein m is 1 and n is 0, and each of the Ar and Ar' is a naphthyl group.
[5] The compound according to claim 1, wherein m is 0 and n is 1, and each of the Ar and Ar' is a phenyl group.
[6] A preparation method of a compound of Formula 1 according to claim 1, comprising reacting an amine compound represented by Formula 2 with a compound represented by Formula 3: Formula 1
wherein m and n are O or 1, respectively;
B represents a nitrogen atom in case of n=0; A represents a carbon atom and B represents CH in case of n=l ;
Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R, CH and SiR , or may be directly connected to each other without a linker; R and R' are independently selected from the group consisting of hydrogen, deuterium, CN, F and CH ; provided that the compound of Formula 1 essentially has one or more deuterium within a molecule.
[7] A preparation method of the compound of Formula 1 according to claim 1 , comprising:
(1) reacting an amine compound represented by Formula 2 with a compound represented by Formula 4 to obtain a compound represented by Formula 5; and
(2) coupling the compound of Formula 5 with each other to obtain a compound of Formula 5:
Formula 1
Formula 2 Ar — NH-Ar' Formula 4
Formula 5
V-<T )VCHO
Ar wherein m and n are O or 1, respectively;
B represents a nitrogen atom in case of n=0; A represents a carbon atom and B represents CH in case of n=l ;
Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R, CH and SiR , or may be directly connected to each other without a linker; and R and R' are independently selected from the group consisting of hydrogen , deuterium, CN, F and CH ; provided that the compound of Formula 1 essentially has one or more deuterium within a molecule.
[8] A preparation method of a compound of Formula 1 according to claim 1, comprising:
(a) converting a compound represented by Formula 6 into an activated phophonate compound; and
(b) reacting the activated phosphonate compound with benzophenone to obtain the compound of Formula 1:
Formula 1
Formula 6
B represents a nitrogen atom in case of n=0; A represents a carbon atom and B represents CH in case of n=l ;
Ar and Ar' are independently the same as or different from each other and represent an aromatic group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, carbazole and fluorenyl which may optionally be substituted with deuterium, CN, F, Cl or Br; wherein Ar and Ar' may be connected to each other by means of a linker selected from the group consisting of S, N-aryl, N-R, CH and SiR , or may be directly connected to each other without a linker; R and R' are independently selected from the group consisting of hydrogen, deuterium, CN, F and CH ; provided that the compound of Formula 1 essentially has one or more deuterium within a molecule.
[9] An organic light emitting diode comprising the compound according to any one of claims 1 to 5.
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| KR1020050033339A KR100676966B1 (en) | 2005-04-21 | 2005-04-21 | Deuterated organic electroluminescence material, preparation method thereof and organic light emitting diode using the same |
| KR10-2005-0033339 | 2005-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2005/003840 WO2006112582A1 (en) | 2005-04-21 | 2005-11-11 | Deuterated organic electroluminescent material, preparation method thereof and organic light emitting diode using the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100676966B1 (en) |
| WO (1) | WO2006112582A1 (en) |
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| WO2008117889A1 (en) * | 2007-03-28 | 2008-10-02 | Fujifilm Corporation | Organic electroluminescent device |
| EP1995292A1 (en) * | 2007-05-18 | 2008-11-26 | FUJIFILM Corporation | Organic electroluminescent device |
| JP2009076865A (en) * | 2007-08-29 | 2009-04-09 | Fujifilm Corp | Organic electroluminescence device |
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| US20100081846A1 (en) * | 2007-01-26 | 2010-04-01 | Doosan Corporation | Asymmetric styryl derivatives and organic light emitting diode prepared using the same |
| WO2011087811A3 (en) * | 2009-12-21 | 2011-11-17 | E. I. Du Pont De Nemours And Company | Electroactive composition and electronic device made with the composition |
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| EP1995292A1 (en) * | 2007-05-18 | 2008-11-26 | FUJIFILM Corporation | Organic electroluminescent device |
| JP2009076865A (en) * | 2007-08-29 | 2009-04-09 | Fujifilm Corp | Organic electroluminescence device |
| US8263973B2 (en) | 2008-12-19 | 2012-09-11 | E I Du Pont De Nemours And Company | Anthracene compounds for luminescent applications |
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| CN102695777B (en) * | 2009-12-21 | 2015-11-25 | E·I·内穆尔杜邦公司 | Electroactive composition and the electron device obtained by said composition |
| WO2011087811A3 (en) * | 2009-12-21 | 2011-11-17 | E. I. Du Pont De Nemours And Company | Electroactive composition and electronic device made with the composition |
| CN102695777A (en) * | 2009-12-21 | 2012-09-26 | E·I·内穆尔杜邦公司 | Electroactive composition and electronic device made with the composition |
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| TWI586638B (en) * | 2012-07-25 | 2017-06-11 | 三星顯示器有限公司 | Condensed-cyclic compound and organic light-emitting device including the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100676966B1 (en) | 2007-02-02 |
| KR20060111048A (en) | 2006-10-26 |
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