JP4327443B2 - Phenanthroline derivatives and uses thereof - Google Patents
Phenanthroline derivatives and uses thereof Download PDFInfo
- Publication number
- JP4327443B2 JP4327443B2 JP2002341267A JP2002341267A JP4327443B2 JP 4327443 B2 JP4327443 B2 JP 4327443B2 JP 2002341267 A JP2002341267 A JP 2002341267A JP 2002341267 A JP2002341267 A JP 2002341267A JP 4327443 B2 JP4327443 B2 JP 4327443B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl group
- aryl
- phenanthroline
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000005041 phenanthrolines Chemical class 0.000 title description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 29
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 13
- MSTUPORHCFOHOX-UHFFFAOYSA-N 3,8-dinaphthalen-1-yl-1,10-phenanthroline Chemical compound C1=CC=C2C(C=3C=C4C=CC=5C(C4=NC=3)=NC=C(C=5)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 MSTUPORHCFOHOX-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 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 10
- 239000010409 thin film Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002019 doping agent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- MIVQFAGNZABSKD-UHFFFAOYSA-N C1=CC=C2C=C3C(=CC2=C1)C=CC=C3C4=CN=C5C(=C4)C=CC6=CC(=CN=C65)C7=CC=CC8=CC9=CC=CC=C9C=C87 Chemical compound C1=CC=C2C=C3C(=CC2=C1)C=CC=C3C4=CN=C5C(=C4)C=CC6=CC(=CN=C65)C7=CC=CC8=CC9=CC=CC=C9C=C87 MIVQFAGNZABSKD-UHFFFAOYSA-N 0.000 description 7
- -1 aryl compound Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- ZSFMMIUNHZSEDS-UHFFFAOYSA-N 3,8-dinaphthalen-2-yl-1,10-phenanthroline Chemical compound c1ccc2cc(ccc2c1)-c1cnc2c(ccc3cc(cnc23)-c2ccc3ccccc3c2)c1 ZSFMMIUNHZSEDS-UHFFFAOYSA-N 0.000 description 5
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 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 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 3
- 0 COc1c(*(CCC2)P3(Oc4c(*(*)CCC5)c5ccc4)Oc4cccc5c4*3CCC5)c2ccc1 Chemical compound COc1c(*(CCC2)P3(Oc4c(*(*)CCC5)c5ccc4)Oc4cccc5c4*3CCC5)c2ccc1 0.000 description 3
- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- FUYYZRSYMOGBMW-UHFFFAOYSA-N 2,3-dibromo-1,10-phenanthroline Chemical compound C1=CC=NC2=C(N=C(C(Br)=C3)Br)C3=CC=C21 FUYYZRSYMOGBMW-UHFFFAOYSA-N 0.000 description 2
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005427 anthranyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- VXLQXFQDOGUAPA-UHFFFAOYSA-N (4-methoxyphenyl)phosphane Chemical compound COC1=CC=C(P)C=C1 VXLQXFQDOGUAPA-UHFFFAOYSA-N 0.000 description 1
- NDLHUHRGAIHALB-UHFFFAOYSA-N 1,10-phenanthrolin-10-ium;chloride;hydrate Chemical compound O.Cl.C1=CN=C2C3=NC=CC=C3C=CC2=C1 NDLHUHRGAIHALB-UHFFFAOYSA-N 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- GBHRGHJTZFOAKE-UHFFFAOYSA-N 2-anthracen-9-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=C(C=CC=C2)C2=CC2=CC=CC=C12 GBHRGHJTZFOAKE-UHFFFAOYSA-N 0.000 description 1
- IDWJREBUVYSPKS-UHFFFAOYSA-N 3,8-dibromo-1,10-phenanthroline Chemical compound BrC1=CN=C2C3=NC=C(Br)C=C3C=CC2=C1 IDWJREBUVYSPKS-UHFFFAOYSA-N 0.000 description 1
- SPPZBAGKKBHZRW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-naphthalen-2-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=CC=C2)C2=C1 SPPZBAGKKBHZRW-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XPHBRTNHVJSEQD-UHFFFAOYSA-N anidoxime Chemical group C=1C=CC=CC=1C(CCN(CC)CC)=NOC(=O)NC1=CC=C(OC)C=C1 XPHBRTNHVJSEQD-UHFFFAOYSA-N 0.000 description 1
- VZXHRGOVLMIZLL-UHFFFAOYSA-N anthracen-9-yloxyboronic acid Chemical compound C1=CC=C2C(OB(O)O)=C(C=CC=C3)C3=CC2=C1 VZXHRGOVLMIZLL-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- BINBUVDYVMWEGQ-UHFFFAOYSA-N dimethoxy(methyl)borane Chemical compound COB(C)OC BINBUVDYVMWEGQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Images
Description
【０００１】
【発明の属する技術分野】
本発明は、新規なフェナントロリン誘導体、それよりなる電子輸送材料およびそれを用いた有機ＥＬ素子に関する。
【０００２】
【従来技術】
従来、下記式、
【化７】
しかし、Ａｌｑ３は効率のよい電子輸送材料であるが、このものを使用すると本来緑色の発光材料であるから、緑色に発光する。しかし緑色より短い波長たとえば青色を取り出したい場合にはＡｌｑ３は使用することができない。そこで大きなバンドギャップをもつバソフェナンソロジン（ＢＰｈｅｎ）や下記式
【化８】
【０００３】
【発明が解決しようとする課題】
本発明の目的は、Ａｌｑ３に優るとも劣らない電子輸送性能を示す新規なフェナントロリン誘導体およびその用途を提供する点にある。
【０００４】
【課題を解決するための手段】
本発明の第１は、下記一般式（１）
【化９】
【化１０】
よりなる群からそれぞれ独立して選ばれた基であり、Ｑは
【化１１】
【化１２】
よりなる群からそれぞれ独立して選ばれた基である。〕
よりなる群から選ばれた２環以上の芳香族基であることを特徴とするフェナントロリン誘導体に関する。
本発明の第２は、請求項１記載のフェナントロリン誘導体が下記式、
【化１３】
【化１４】
本発明の第３は、請求項１または２記載のフェナントロリン誘導体よりなることを特徴とする電子輸送材料に関する。
本発明の第４は、請求項１または２記載のフェナントロリン誘導体を含有する電子輸送層をもつことを特徴とする有機ＥＬ素子に関する。
【０００５】
本発明の有機エレクトロルミネッセンス素子に使用する一般式（１）の化合物のフェナントロリン誘導体は、アリール基、好ましくはナフチル基、アントラニル基、より好ましくはアントラニル基により、耐熱凝集性の少ないキャリアー輸送性を発揮することができる。また、中心の分子がフェナントロリン環であることから高い電子輸送性を示すことは明らかである。
【０００６】
一般式（１）で示される本発明の化合物であるフェナントロリン誘導体を製造するための方法は前記一般式（１）におけるＱが結合している部位はＲ１、Ｒ４、Ｒ５、Ｒ６が結合している部位に較べて反応性が大変低いため、反応試薬の選定および場合により反応条件の設定に多大の工夫を要する。その１つの方法は、下記一般式（２）
【化１５】
【化１６】
よりなる群からそれぞれ独立して選ばれた基である。〕
で示される３,８−ジハロゲン化フェナントロリンと一般式（３）、
【化１７】
【化１８】
【化１９】
よりなる群からそれぞれ独立して選ばれた基である。〕
で示されるホウ素化アリール化合物とを反応させる方法である。
とくに好ましい方法の１つは、一般式（２）で示される３，８−ジハロゲン化フェナントロリンと下記一般式（４）
【化２０】
で示されるホウ素化アリール化合物とを反応させる方法であるが、この場合は、一般式（２）の化合物、一般式（４）の化合物およびＰｄ〔Ｐ（Ｐｈ）３〕４〔ただしＰｈはフェニル基を指す。〕をジメチルホルムアミド（ＤＭＦ）などの溶剤に溶解させ、ここに炭酸カリウム水溶液のようなアルカリ成分を添加して反応を進行させることができる。
【０００７】
一般式（１）で示される本発明の化合物であるフェナントロリン誘導体を製造するためのもう１つの好ましい方法は、一般式（２）で示される３，８−ジハロゲン化フェナントロリンと下記一般式（５）
【化２１】
で示される水酸基含有ホウ素化アリール化合物とを反応させる方法である。これらの場合は、一般式（２）の化合物と例えばＣｈｅｍ．Ｒｅｖ．１９９５，９５，２４５７〜２４８３あるいはＴｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，ｖｏｌ．３８，Ｎｏ．１９，Ｐ３４４７〜３４５０，１９９７に例示された方法で一般式（３）〜（５）の化合物をジメチルホルムアミド（ＤＭＦ）のような溶剤に溶かし、不活性ガス雰囲気下に触媒（たとえば有機リン系パラジウム触媒）と塩基（たとえばＫ３ＰＯ４、Ｋ２ＣＯ３、ナトリウムアルコラート、重曹などのアルカリ金属またはアルカリ土類金属の塩）の存在下で反応を行うことができる。
有機リン系パラジウム触媒としては特に下記式
【化２２】
で示されるアリールリン系パラジウム触媒が好ましい。
具体的にはＡｒ１〜Ａｒ３がすべてフェニル基のものやＡｒ１がフェニル基でＡｒ２、Ａｒ３がトリル基であるものなどを例示することができる。
具体的に言えば、テトラキス（トリフェニルホスフィン）パラジウム、テトラキス（トリ４−メチルフェニルホスフィン）パラジウム、テトラキス（トリ３−メチルフェニルホスフィン）パラジウム、テトラキス（トリ２−メチルフェニルホスフィン）パラジウム、テトラキス（トリ４−メトキシフェニルホスフィン）パラジウム、テトラキス（トリ３−メトキシフェニルホスフィン）パラジウム、テトラキス（トリ２−メトキシフェニルホスフィン）パラジウムなどが例示できるがこれらに限定されるものではない。
【０００８】
これらの反応で使用できる溶媒としてはトルエン、キシレンなどの芳香族溶媒、メタノール、エタノールなどのアルコール系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、１−メチルピロリドンなどの極性溶媒などが挙げられる。これらの溶媒については単独、あるいは混合して使用することができる。またこれらの溶媒に水を混合して使用することもできる。
【０００９】
前記Ｅ１、Ｅ２、Ｑ、Ａ、Ｒ１〜Ｒ ６ 、Ｒ １０ 〜Ｒ ２３ およびＲにおけるアルキル基としては、直鎖または分岐の任意の炭素数のものであることができるが好ましくは炭素数１〜２０のものであり、アリール基としては、縮合環の数が1個または複数のものであり、かつ縮合環にはアルキル置換基（前記アルキル基と同様のことが言える）があってもよく、前記複数とは２〜５個であることが好ましく、アラルキル基としては前記アルキル基とアリール基の任意の組合せによる基であることができ、アルキルアミノ基としては、モノアルキルアミノ基、ジアルキルアミノ基であることができ、各アルキル基は前記と同様のアルキル基であることができる。ただし、これらの置換基の組合せにおいて立体障害が発生しない範囲で選択するのは当然のことである。
【００１０】
本発明の化合物は、ＥＬ素子の電子輸送材料として使用できる。とくに、３，８−ジアントラセニルフェナントロリン（ＤＡｎＰｈｅｎ）は電子輸送兼発光層として有効に機能する。
【００１１】
本発明の化合物を電子輸送層の形成材料として使用したＥＬ素子としては、従来公知の層構成を採用することができる。例えば（イ）陽極／ホール輸送層／発光層／本発明化合物を用いた電子輸送層／電子注入層／陰極、（ロ）陽極／ホール輸送層／発光層／本発明化合物を用いた発光兼電子輸送層／電子注入層／陰極、（ハ）陽極／ホール輸送層／本発明化合物とドーパントからなる発光層／本発明化合物を用いた電子輸送層（電子注入剤を併用することがある）／電子注入層／陰極などの層構成を挙げることができる。
【００１２】
具体的な本発明ＥＬ素子の層構成例を以下に示すが、本発明はこれにより何ら限定されるものではない。
ＩＴＯ／ＮＰＤ／Ａｌｑ３（発光層）／ＤＡｎＰｈｅｎ／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／Ａｌｑ３＋ｄｏｐａｎｔ（発光層）／ＤＡｎＰｈｅｎ
／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／ＤＡｎＰｈｅｎ＋ｄｏｐａｎｔ（発光層）
／ＤＡｎＰｈｅｎ／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／ＤＡｎＰｈｅｎ／ＤａｎＰｈｅｎ／ＬｉＦ／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／Ａｌｑ３（発光層）／ＤＡｎＰｈｅｎ／ＤａｎＰｈｅｎ
＋ＬｉＦ／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／Ａｌｑ３＋ｄｏｐａｎｔ（発光層）／ＤＡｎＰｈｅｎ／
ＤａｎＰｈｅｎ＋ＬｉＦ／ＬｉＦ／Ａｌ
ＩＴＯ／ＮＰＤ／ＤＡｎＰｈｅｎ＋ｄｏｐａｎｔ（発光層）／
ＤａｎＰｈｅｎ＋ＬｉＦ／ＬｉＦ／Ａｌ
なお、ＮＰＤはホール輸送剤Ｎ，Ｎ′−ジ（１−ナフチル）−Ｎ，Ｎ′−ジフェニル−ベンジジンであり、ＤＡｎＰｈｅｎは本発明の３，８−ジアントラセニルフェナントロリンであるが、このかわりに、本発明の他の化合物を用いてもよい。Ａｌｑ３は代表的な発光材料であり、その正式名称と化学構造は従来技術の項で述べたとおりである。ＬｉＦは電子注入層であり、ＬｉＦは電子注入剤として機能している。（ＤＡｎＰｈｅｎ＋ＬｉＦ）の層はＤＡｎＰｈｅｎの層とＬｉＦの層との密着性を向上させるための層であり、このように上下の層の混合物の層を介在させることにより上下層の密着性を向上させる手段は、この分野ではよく行われる。ドーパントは従来公知のものが使用できるが、例えば本発明のＤＡｎＰｈｅｎは緑色に蛍光するからドーパントとしては、緑色から赤色の範囲の色素が使用できる。例えば、緑色の色素としてはキナクリドン、ジメチルキナクリドン、クマリンＣ５４０、クマリンＣ５４５Ｔなどがある。黄色の色素としてはルブレン、赤色の色素としてはナイルレッド、ＤＣＭなどが挙げられる。
なお、実施例１に示す３，８−ジ−（１−ナフチル）フェナントロリン（Ｄ−１ＮａＰｈｅｎ）を用いる場合には、これが青色に蛍光するので青色〜赤色のドーパントが使用できる。青色のドーパントとしては、テトラフェニルブタジエン、ペリレンなどを挙げることができる。
【００１３】
【実施例】
以下に実施例、参考例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。
【００１４】
参考例１
（１）３，８−ジブロモフェナントロリン（ＤＢｒＰｈｅｎ）の合成
【化２３】
【００１５】
（２）９−アントラセニル−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランの合成
【化２４】
【００１６】
（３）３，８−ジアントラセニルフェナントロリン（ＤＡｎＰｈｅｎ）の合成
【化２５】
融点 ３００℃以上、
１Ｈ−ＮＭＲ（ＣＤＣｌ３，ＴＭＳ）δ（ｐｐｍ）９．４，８．５，８．０５（２Ｈ，２Ｈ，２Ｈ，ｐａｒｔ ｏｆ Ｐｈｅｎ），８．６８，８．１７，７．７５，６．００−７．４０（２Ｈ，４Ｈ，８Ｈ，ｐａｒｔ ｏｆ Ａｎｔｈｒａｃｅｎｅ）
【００１７】
実施例１
（１）１−ブロモナフタレンのホウ素化
【化２６】
【００１８】
（２）３，８−ジ−（１−ナフチル）フェナントロリン（Ｄ−１ＮａＰｈｅｎ）の合成
【化２７】
【００１９】
実施例２
（１）２−（２−ナフチル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（２−ＮａＤＯＢ）の合成
【化２８】
【００２０】
（２）３，８−ジ−（２−ナフチル）フェナントロリン（Ｄ−２ＮａＰｈｅｎ）の合成
参考例１の（１）で得られたジブロモ体２．９５ｍｍｏｌ、実施例２の（１）で得られたホウ素体１１．８ｍｍｏｌ、Ｋ３ＰＯ４８．８５ｍｍｏｌ、Ｐｄ〔Ｐ（Ｐｈ）３〕４２０ｍｍｏｌ、トルエン１００ｍｌ、エタノール３０ｍｌ、水５ｍｌを用いて、実施例１の（２）に準じて合成した。同定は、ＩＲスペクトル（図７）、１Ｈ−ＮＭＲスペクトル（図８）で行った。図９の点線は、３，８−ジ−（２−ナフチル）フェナントロリン薄膜の吸収スペクトルを示し、図９の実線は同薄膜の蛍光スペクトルを示す。
【化２９】
参考例２
（１）９−アンスリルボラン酸（９−ＡｂＡ）の合成
【化３０】
ＩＲ（ＫＢｒ，ｃｍ−１）３２８６（−ＯＨ）８８３．２と７２５．１
【００２２】
（２）９−アンスリルボラン酸を用いたジブロモフェナントロリンとのカップリング
【化３１】
【００２３】
実施例３
ＩＴＯ／ＮＰＤ／Ｄ−１ＮａＰｈｅｎ／ＬｉＦ／Ａｌ素子の作成
ＩＴＯ膜よりなる陰極上に、ＮＰＤ〔Ｎ，Ｎ′−ジ−（１−ナフチル）−Ｎ，Ｎ′−ジフェニル−ベンジン〕を５００Å厚に、ついで実施例１で得られたＤ−１ＮａＰｈｅｎ〔３，８−ジ−（１−ナフチル）フェナントロリン〕を６００Å厚に真空蒸着した後、さらにＬｉＦを５Åで、さらにその上にＡｌを１０００Å厚で蒸着し、ＥＬ素子を作成した。
この素子の特性は、図１０に示す。
図１０に示すように、本発明のＥＬ素子は、印加電流の変化によって色合いが微妙に変化するという特異な傾向を示すが、ＮＰＤを用いた素子やＢＣＰ（バソクフロイン）を用いた素子の場合は印加電流が変化しても、グラフが左右に移動することはなく、いいかえれば色相の変化は全く発生しない。
【００２４】
実施例４
ＩＴＯ／ＮＰＤ／Ｄ−２ＮａＰｈｅｎ／ＬｉＦ／Ａｌ素子の作成
ＩＴＯ膜よりなる陰極上に、ＮＰＤを５００Å厚に、ついで実施例２で得られたＤ−２ＮａＰｈｅｎを６００Å厚に真空蒸着した後、さらにＬｉＦを５Åで、さらにその上にＡｌを１０００Å厚で蒸着し、ＥＬ素子を作成した。
この素子の特性は、図１１に示す。
図１１に示すように、この実施例にかかる本発明のＥＬ素子も印加電流に対応してＥＬ素子が変化するが、ＮＰＤやＢＣＰの場合は全く変化がない。
【００２５】
比較例１
参考例１と同様の要領でＩＴＯ／ＮＰＤ（５００Å）／ＢＣＰ（７００Å）／ＬｉＦ（５Å）／Ａｌ（１０００Å）の素子を作成した。
前記ＢＣＰは〔０００２〕で述べたバソクフロイン（ｂａｔｈｏｃｕｐｒｏｉｎｅ）である。
【００２６】
実施例３および４のＥＬ素子と比較例１のＥＬ素子の物性を図１２〜１４に示す。図１２〜１４において、○印は実施例３の素子を、□印は実施例４の素子を、△印は比較例１の素子をそれぞれ示している。図１２はそれぞれのルミネッセンス強度と電圧の関係を、図１３はそれぞれの電流密度の電圧の関係を図１４はそれぞれのルミネッセンス強度と電流密度の関係を示す。
実施例１で得られたα−ＮＰｈｅｎを用いた素子からは、４５０ｎｍ付近にピークを有する水色発光が観察され、最高輝度３６００ｃｄ／ｍ２＠１２．５Ｖ、最大視感効率０．４４ｌｍ／Ｗ＠８．５Ｖ、最大電流効率１．２２ｃｄ／Ａ（印加電圧８．５Ｖ）、外部量子効率０．８１％であった。また、図１０からわかるように電流量により若干短波長に変化した。これらのＥＬスペクトルはＮＰＤやＤ−１ＮａＰｈｅｎのＰＬスペクトル（λｍａｘ＝４００ｎｍ）とも一致していないため、ＮＰＤとＤ−１ＮａＰｈｅｎのエキシプレックスからの発光と考えられ、高電流密度下において再結合領域が変化していることが考えられる。
実施例２で得られたＤ−２ＮａＰｈｅｎを用いた素子では、５００ｎｍ付近にピークを有するややブロードな発光が得られ、最高輝度３１００ｃｄ／ｍ２＠９．５Ｖ、最大視感効率０．５３ｌｍ／Ｗ＠７．５Ｖ、最大電流効率１．３２ｃｄ／Ａ＠８Ｖ、最大外部量子効率０．６１％であった。このＥＬスペクトルも図１１にみられるように電流量に依存してスペクトルが変化した。これもＤ−１ＮａＰｈｅｎ同様ＮＰＤとのエキシプレックスと考えられ、４５０ｎｍ付近のショルダーの増大から高電流密度下においてＮＰＤ側に再結合領域が広がっていると考えられる。
比較のため、ＢＣＰを用いた素子も作製しグラフに載せている。
【００２７】
【発明の効果】
（１）本発明により、Ａｌｑ３に優るとも劣らない電子輸送性能を示す新規な材料を提供することができた。
（２）本発明により、新しい電子輸送材料を用いたＥＬ素子を提供することができた。
【図面の簡単な説明】
【図１】 参考例１で得られた３，８−ジアントラセニルフェナントロリンのＩＲスペクトル図である。
【図２】 参考例１で得られた３，８−ジアントラセニルフェナントロリンの１Ｈ−ＮＭＲスペクトル図である。
【図３】 点線は、参考例１で得られた３，８−ジアントラセニルフェナントロリンよりなる薄膜の吸収スペクトル図であり、実線は同薄膜の蛍光スペクトル図である。
【図４】 実施例１で得られた３，８−ジ−（１−ナフチル）フェナントロリンのＩＲスペクトル図である。
【図５】 実施例１で得られた３，８−ジ−（１−ナフチル）フェナントロリンの１Ｈ−ＮＭＲスペクトル図である。
【図６】 点線は、実施例１で得られた３，８−ジ−（１−ナフチル）フェナントロリンよりなる薄膜の吸収スペクトル図であり、実線は同薄膜の蛍光スペクトル図である。
【図７】 実施例２で得られた３，８−ジ−（２−ナフチル）フェナントロリンのＩＲスペクトル図である。
【図８】 実施例２で得られた３，８−ジ−（２−ナフチル）フェナントロリンの１Ｈ−ＮＭＲスペクトル図である。
【図９】 点線は、実施例２で得られた３，８−ジ−（２−ナフチル）フェナントロリンよりなる薄膜の吸収スペクトル図であり、実線は同薄膜の蛍光スペクトル図である。
【図１０】 実施例３のＥＬ素子のエレクトロルミネッセンス強度と波長の関係を示すグラフである。
【図１１】 実施例４のＥＬ素子のエレクトロルミネッセンス強度と波長の関係を示すグラフである。
【図１２】 実施例３（○印）、実施例４（□印）、比較例１（△印）のルミネッセンス強度と電圧の関係を示すグラフである。
【図１３】 実施例３（○印）、実施例４（□印）、比較例１（△印）の電流密度と電圧の関係を示すグラフである。
【図１４】 実施例３（○印）、実施例４（□印）、比較例１（△印）のルミネッセンス強度と電流密度の関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel phenanthroline derivative, an electron transport material comprising the same, and an organic EL device using the sameAbout.
[0002]
[Prior art]
Conventionally, the following formula,
[Chemical 7]
However, Alq3Is an efficient electron transport material, but when this material is used, it is a green light-emitting material, so it emits green light. However, when it is desired to extract a wavelength shorter than green, for example, blue, Alq3Can not be used. Therefore, Vasophenanthorozin (BPhen) with a large band gap and the following formula
[Chemical 8]
[0003]
[Problems to be solved by the invention]
The object of the present invention is to provide Alq3Novel phenanthroline derivative with electron transport performance comparable to or better thanAnd their usesIs to provide
[0004]
[Means for Solving the Problems]
The first of the present invention is the following general formula (1)
[Chemical 9]
[Chemical Formula 10]
Each independently selected from the group consisting of:Q is
Embedded image
Embedded image
Each independently selected from the group consisting of: ]
It is an aromatic group having two or more rings selected from the group consisting ofIt relates to phenanthroline derivatives.
First of the present invention2Wherein the phenanthroline derivative according to claim 1 is represented by the following formula:
Embedded image
Embedded image
First of the present invention3Claim 1Or 2The present invention relates to an electron transport material comprising the phenanthroline derivative described above.
First of the present invention4Claim 1Or 2The present invention relates to an organic EL device having an electron transport layer containing the described phenanthroline derivative.
[0005]
The phenanthroline derivative of the compound of the general formula (1) used for the organic electroluminescence device of the present invention exhibits carrier transport properties with little heat aggregation property due to an aryl group, preferably a naphthyl group, an anthranyl group, more preferably an anthranyl group. can do. In addition, since the central molecule is a phenanthroline ring, it is clear that it exhibits high electron transport properties.
[0006]
The method for producing the phenanthroline derivative, which is the compound of the present invention represented by the general formula (1), is the site where Q in the general formula (1) is bonded to R.1, R4, R5, R6Since the reactivity is very low compared with the site | part which has couple | bonded, selection of a reaction reagent and the setting of reaction conditions depending on the case require a lot of contrivance. One way isThe following general formula (2)
Embedded image
Embedded image
Each independently selected from the group consisting of: ]
3,8-dihalogenated phenanthroline represented by the general formula (3),
Embedded image
Embedded image
Embedded image
Each independently selected from the group consisting of: ]
It is a method of reacting with a boronated aryl compound represented by.
One particularly preferred method is3,8-dihalogenated phenanthroline represented by the general formula (2)followingGeneral formula (4)
Embedded image
In this case, the compound of the general formula (2), the compound of the general formula (4) and Pd [P (Ph)3]4[However, Ph represents a phenyl group. ] Can be dissolved in a solvent such as dimethylformamide (DMF), and an alkali component such as an aqueous potassium carbonate solution can be added thereto to allow the reaction to proceed.
[0007]
Another preferred method for producing the phenanthroline derivative which is the compound of the present invention represented by the general formula (1) is a 3,8-dihalogenated phenanthroline represented by the general formula (2):followingGeneral formula (5)
Embedded image
In which a hydroxyl group-containing arylated boron compound is reacted. In these cases, compounds of general formula (2) and for example Chem. Rev. 1995, 95, 2457-2483 or Tetrahedron Letters, vol. 38, no. 19, P3447-3450, 1997. The compounds of the general formulas (3) to (5) are dissolved in a solvent such as dimethylformamide (DMF), and the catalyst (for example, organophosphorus palladium is used in an inert gas atmosphere. Catalyst) and base (eg K)3PO4, K2CO3In the presence of an alkali metal or alkaline earth metal salt such as sodium alcoholate or sodium bicarbonate.
Especially as organophosphorus palladium catalyst
Embedded image
An aryl phosphorus-based palladium catalyst represented by
Specifically, Ar1~ Ar3Are all phenyl groups or Ar1Is a phenyl group and Ar2, Ar3Can be exemplified by those in which is a tolyl group.
Specifically, tetrakis (triphenylphosphine) palladium, tetrakis (tri-4-methylphenylphosphine) palladium, tetrakis (tri-3-methylphenylphosphine) palladium, tetrakis (tri-2-methylphenylphosphine) palladium, tetrakis (tri Examples thereof include, but are not limited to, 4-methoxyphenylphosphine) palladium, tetrakis (tri-3-methoxyphenylphosphine) palladium, and tetrakis (tri-2-methoxyphenylphosphine) palladium.
[0008]
Examples of the solvent that can be used in these reactions include aromatic solvents such as toluene and xylene, alcohol solvents such as methanol and ethanol, and polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and 1-methylpyrrolidone. These solvents can be used alone or in combination. These solvents can also be used by mixing water.
[0009]
E1, E2, Q, A, R1~R 6 , R 10 ~ R 23 And the alkyl group in R can be linear or branched having any number of carbon atoms, but preferably has 1 to 20 carbon atoms, and the aryl group has one condensed ring or And the condensed ring may have an alkyl substituent (which can be said to be the same as the alkyl group), and the plurality is preferably 2 to 5, and the aralkyl group includes The alkylamino group can be a monoalkylamino group or a dialkylamino group, and each alkyl group is the same alkyl group as described above. Can do. However, it is a matter of course that the combination of these substituents is selected in such a range that steric hindrance does not occur.
[0010]
The compound of the present invention can be used as an electron transport material for EL devices. In particular, 3,8-dianthracenylphenanthroline (DAnPhen) functions effectively as an electron transporting / emitting layer.
[0011]
A conventionally well-known layer structure can be employ | adopted as an EL element which uses the compound of this invention as a forming material of an electron carrying layer. For example, (a) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode using the compound of the present invention, and (b) anode / hole transport layer / light emitting layer / light emitting / electron using the compound of the present invention. Transport layer / electron injection layer / cathode, (c) anode / hole transport layer / light emitting layer comprising the compound of the present invention and a dopant / electron transport layer using the compound of the present invention (electron injection agent may be used in combination) / electron Examples of the layer structure include an injection layer / a cathode.
[0012]
Specific examples of the layer structure of the EL element of the present invention are shown below, but the present invention is not limited thereto.
ITO / NPD / Alq3(Light emitting layer) / DAnPhen / LiF / Al
ITO / NPD / Alq3+ Dopant (light emitting layer) / DAnPhen
/ LiF / Al
ITO / NPD / DAnPhen + dopant (light emitting layer)
/ DAnPhen / LiF / Al
ITO / NPD / DAnPhen / DanPhen / LiF / LiF / Al
ITO / NPD / Alq3(Light emitting layer) / DAnPhen / DanPhen
+ LiF / LiF / Al
ITO / NPD / Alq3+ Dopant (light emitting layer) / DAnPhen /
DanPhen + LiF / LiF / Al
ITO / NPD / DAnPhen + dopant (light emitting layer) /
DanPhen + LiF / LiF / Al
NPD is the hole transport agent N, N′-di (1-naphthyl) -N, N′-diphenyl-benzidine, and DAnPhen is the 3,8-dianthracenylphenanthroline of the present invention. Other compounds of the present invention may be used. Alq3Is a typical luminescent material, and its formal name and chemical structure are as described in the section of the prior art. LiF is an electron injection layer, and LiF functions as an electron injection agent. The (DAnPhen + LiF) layer is a layer for improving the adhesion between the DAnPhen layer and the LiF layer, and means for improving the adhesion between the upper and lower layers by interposing a mixture of the upper and lower layers in this way. Is often done in this area. A conventionally well-known thing can be used for a dopant, For example, since DAnPhen of this invention fluoresces green, as a dopant, the pigment | dye of the range of green to red can be used. For example, green pigments include quinacridone, dimethylquinacridone, coumarin C540, and coumarin C545T. Examples of yellow pigments include rubrene, and examples of red pigments include Nile Red and DCM.
In addition,Example 1In the case of using 3,8-di- (1-naphthyl) phenanthroline (D-1NaPhen) as shown in FIG. 4, since it fluoresces blue, a blue to red dopant can be used. Examples of the blue dopant include tetraphenylbutadiene and perylene.
[0013]
【Example】
Examples belowReference examplesHowever, the present invention is not limited to these examples.
[0014]
referenceExample 1
(1) Synthesis of 3,8-dibromophenanthroline (DBrPhen)
Embedded image
[0015]
(2) Synthesis of 9-anthracenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Embedded image
[0016]
(3) Synthesis of 3,8-dianthracenylphenanthroline (DAnPhen)
Embedded image
1H-NMR (CDCl3, TMS) δ (ppm) 9.4, 8.5, 8.05 (2H, 2H, 2H, part of Phen), 8.68, 8.17, 7.75, 6.00-7.40 ( 2H, 4H, 8H, part of Anthracene)
[0017]
Example1
(1) Boronation of 1-bromonaphthalene
Embedded image
[0018]
(2) Synthesis of 3,8-di- (1-naphthyl) phenanthroline (D-1NaPhen)
Embedded image
[0019]
Example2
(1) Synthesis of 2- (2-naphthyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-NaDOB)
Embedded image
[0020]
(2) Synthesis of 3,8-di- (2-naphthyl) phenanthroline (D-2NaPhen)
reference2.95 mmol of dibromo compound obtained in (1) of Example 1, Example2Boron body obtained in (1) of 11.8 mmol, K3PO48.85 mmol, Pd [P (Ph)3]4Example using 20 mmol,
Embedded image
referenceExample2
(1) Synthesis of 9-anthrylboronic acid (9-AbA)
Embedded image
IR (KBr, cm-1) 3286 (-OH) 883.2 and 725.1
[0022]
(2) Coupling with dibromophenanthroline using 9-anthrylboronic acid
Embedded image
[0023]
Example3
Creation of ITO / NPD / D-1NaPhen / LiF / Al element
An NPD [N, N'-di- (1-naphthyl) -N, N'-diphenyl-benzine] is formed to a thickness of 500 mm on a cathode made of an ITO film, and then an example.1The D-1NaPhen [3,8-di- (1-naphthyl) phenanthroline] obtained in 1) was vacuum-deposited to a thickness of 600 mm, LiF was further evaporated to 5 mm, and Al was further deposited to a thickness of 1000 mm to obtain an EL element. It was created.
The characteristics of this element are shown in FIG.
As shown in FIG. 10, the EL element of the present invention shows a unique tendency that the hue slightly changes due to the change in applied current. However, in the case of an element using NPD or an element using BCP (Bathoc Freon). Even if the applied current changes, the graph does not move to the left or right. In other words, the hue does not change at all.
[0024]
Example4
Creation of ITO / NPD / D-2NaPhen / LiF / Al element
On the cathode made of an ITO film, NPD is made to a thickness of 500 mm, followed by an example.2The D-2NaPhen obtained in (1) was vacuum-deposited to a thickness of 600 mm, further LiF was vapor-deposited at a thickness of 5 mm, and Al was further deposited thereon to a thickness of 1000 mm to produce an EL device.
The characteristics of this element are shown in FIG.
As shown in FIG. 11, the EL element of the present invention according to this example also changes in response to the applied current, but there is no change in the case of NPD or BCP.
[0025]
Comparative Example 1
referenceIn the same manner as in Example 1, an element of ITO / NPD (500 Å) / BCP (700 Å) / LiF (5 Å) / Al (1000 Å) was prepared.
The BCP is the bathocuproine described in [0002].
[0026]
Example3and4The physical properties of the EL element and the EL element of Comparative Example 1 are shown in FIGS. 12-14, ○ mark is an Example3□ is the example4The Δ mark indicates the element of Comparative Example 1. 12 shows the relationship between each luminescence intensity and voltage, FIG. 13 shows the relationship between each current density voltage, and FIG. 14 shows the relationship between each luminescence intensity and current density.
Example1From the device using α-NPhen obtained in the above, light emission having a peak near 450 nm was observed, and the maximum luminance was 3600 cd / m.2@ 12.5 V, maximum luminous efficiency 0.44 lm / W @ 8.5 V, maximum current efficiency 1.22 cd / A (applied voltage 8.5 V), and external quantum efficiency 0.81%. Further, as can be seen from FIG. 10, the wavelength changed slightly depending on the amount of current. Since these EL spectra do not match the PL spectra (λmax = 400 nm) of NPD or D-1NaPhen, it is considered that the light is emitted from the exciplex of NPD and D-1NaPhen, and the recombination region changes under high current density. It is possible that
Example2In the element using D-2NaPhen obtained in Step 1, a slightly broad light emission having a peak in the vicinity of 500 nm is obtained, and the maximum luminance is 3100 cd / m.2@ 9.5V, maximum luminous efficiency 0.53lm/W@7.5V, maximum current efficiency 1.32cd/A@8V, and maximum external quantum efficiency 0.61%. The EL spectrum also changed depending on the amount of current as seen in FIG. This is also considered to be an exciplex with NPD like D-1NaPhen, and it is considered that the recombination region spreads on the NPD side under a high current density due to an increase in shoulder near 450 nm.
For comparison, an element using BCP is also produced and placed on the graph.
[0027]
【The invention's effect】
(1) According to the present invention, Alq3It was possible to provide a novel material exhibiting an electron transport performance which is not inferior to that of the material.
(2) According to the present invention, an EL device using a new electron transport material could be provided.
[Brief description of the drawings]
[Figure 1]reference2 is an IR spectrum diagram of 3,8-dianthracenylphenanthroline obtained in Example 1. FIG.
[Figure 2]referenceOf 3,8-dianthracenylphenanthroline obtained in Example 11It is a H-NMR spectrum figure.
[Figure 3] The dotted linereferenceIt is an absorption spectrum figure of the thin film which consists of 3,8- dianthracenyl phenanthroline obtained in Example 1, and a continuous line is a fluorescence spectrum figure of the same thin film.
FIG. 4 Example1FIG. 3 is an IR spectrum diagram of 3,8-di- (1-naphthyl) phenanthroline obtained in 1.
FIG. 5 Example1Of 3,8-di- (1-naphthyl) phenanthroline obtained in1It is a H-NMR spectrum figure.
FIG. 6 shows a dotted line.12 is an absorption spectrum diagram of a thin film made of 3,8-di- (1-naphthyl) phenanthroline obtained in 1 above, and a solid line is a fluorescence spectrum diagram of the same thin film.
FIG. 7 Example2FIG. 3 is an IR spectrum diagram of 3,8-di- (2-naphthyl) phenanthroline obtained in 1.
FIG. 8 Example2Of 3,8-di- (2-naphthyl) phenanthroline obtained in1It is a H-NMR spectrum figure.
FIG. 9 shows a dotted line in the example.22 is an absorption spectrum diagram of a thin film made of 3,8-di- (2-naphthyl) phenanthroline obtained in 1 above, and a solid line is a fluorescence spectrum diagram of the same thin film.
FIG. 10 Example3It is a graph which shows the electroluminescence intensity | strength of wavelength EL element, and the relationship of a wavelength.
FIG. 11 Example4It is a graph which shows the electroluminescence intensity | strength of wavelength EL element, and the relationship of a wavelength.
FIG. 12 Example3(○), Example4It is a graph which shows the relationship between the luminescence intensity and voltage of Comparative Example 1 (Δ mark).
FIG. 13 Example3(○), Example4It is a graph which shows the relationship between the current density of Comparative Example 1 (triangle | delta), and a voltage.
FIG. 14 Example3(○), Example4It is a graph which shows the relationship between the luminescence intensity and current density of (□ mark) and Comparative Example 1 (Δ mark).
Claims (4)
よりなる群からそれぞれ独立して選ばれた基であり、Ｑは
よりなる群からそれぞれ独立して選ばれた基である。〕
よりなる群から選ばれた２環以上の芳香族基であることを特徴とするフェナントロリン誘導体。The following general formula (1)
Each independently selected from the group consisting of: Q is
Each independently selected from the group consisting of: ]
A phenanthroline derivative, which is an aromatic group having two or more rings selected from the group consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002341267A JP4327443B2 (en) | 2002-11-25 | 2002-11-25 | Phenanthroline derivatives and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002341267A JP4327443B2 (en) | 2002-11-25 | 2002-11-25 | Phenanthroline derivatives and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004175691A JP2004175691A (en) | 2004-06-24 |
| JP4327443B2 true JP4327443B2 (en) | 2009-09-09 |
Family
ID=32703681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002341267A Expired - Fee Related JP4327443B2 (en) | 2002-11-25 | 2002-11-25 | Phenanthroline derivatives and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4327443B2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006004138A1 (en) * | 2004-07-07 | 2006-01-12 | Semiconductor Energy Laboratory Co., Ltd. | Phenanthroline derivative and light emitting element and light emitting device using the same |
| JP5317386B2 (en) | 2005-08-05 | 2013-10-16 | 出光興産株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescence device using the same |
| JP4842587B2 (en) * | 2005-08-11 | 2011-12-21 | 株式会社半導体エネルギー研究所 | Phenanthroline derivative compound, and electron transporting material, light-emitting element, light-emitting device, and electronic device using the same |
| US9666826B2 (en) | 2005-11-30 | 2017-05-30 | Global Oled Technology Llc | Electroluminescent device including an anthracene derivative |
| US7553558B2 (en) * | 2005-11-30 | 2009-06-30 | Eastman Kodak Company | Electroluminescent device containing an anthracene derivative |
| US8420229B2 (en) | 2007-10-26 | 2013-04-16 | Global OLED Technologies LLC | OLED device with certain fluoranthene light-emitting dopants |
| US8431242B2 (en) | 2007-10-26 | 2013-04-30 | Global Oled Technology, Llc. | OLED device with certain fluoranthene host |
| US8076009B2 (en) | 2007-10-26 | 2011-12-13 | Global Oled Technology, Llc. | OLED device with fluoranthene electron transport materials |
| US7931975B2 (en) | 2008-11-07 | 2011-04-26 | Global Oled Technology Llc | Electroluminescent device containing a flouranthene compound |
| US8088500B2 (en) | 2008-11-12 | 2012-01-03 | Global Oled Technology Llc | OLED device with fluoranthene electron injection materials |
| CN103288825A (en) * | 2012-02-27 | 2013-09-11 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing phenanthroline and preparation method and application thereof |
| KR102244374B1 (en) | 2013-08-09 | 2021-04-26 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element, display module, lighting module, light-emitting device, display device, electronic device, and lighting device |
| TWI790559B (en) | 2013-08-09 | 2023-01-21 | 日商半導體能源研究所股份有限公司 | Light-emitting element, display module, lighting module, light-emitting device, display device, electronic device, and lighting device |
| JP2016082239A (en) | 2014-10-16 | 2016-05-16 | 株式会社半導体エネルギー研究所 | Light emitting element, light emitting device, electronic apparatus and lighting device |
| KR102420082B1 (en) | 2015-04-13 | 2022-07-13 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light-emitting device comprising the same |
| CN110283172A (en) * | 2019-07-23 | 2019-09-27 | 武汉华星光电半导体显示技术有限公司 | Optical coupling output material and preparation method thereof, electroluminescent device |
-
2002
- 2002-11-25 JP JP2002341267A patent/JP4327443B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004175691A (en) | 2004-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6869402B2 (en) | Nitrogen-containing compounds, organic electroluminescence devices and photoelectric conversion devices | |
| JP6807341B2 (en) | Amine derivatives, organic luminescent materials and organic electroluminescent devices using them | |
| TWI589562B (en) | Spirobifluorene compounds for light emitting devices | |
| JP4328801B2 (en) | Fluorene compound and organic electroluminescence device | |
| KR100843819B1 (en) | Anthracene derivatives and organic electroluminescent devices made by using the same | |
| KR100812178B1 (en) | Electroluminescent compounds comprising fluorene group and organic electroluminescent device using the same | |
| JP4327443B2 (en) | Phenanthroline derivatives and uses thereof | |
| CN107408636B (en) | Organic electroluminescence device | |
| KR101792175B1 (en) | Spiro compound and organic electroluminescent devices comprising the same | |
| JP6580613B2 (en) | Lighting for plant cultivation using a novel triazine compound | |
| TW201114880A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| JP7193649B2 (en) | Compounds for organic light-emitting devices and long-lived organic light-emitting devices containing the same | |
| JP4350960B2 (en) | 4,4 ″ -di- (aryl) -3 ′, 4 ′, 5 ′, 6′-tetraphenyl-p-terphenyl derivative, host material comprising the same, and electroluminescence device using the same | |
| JP2005112856A (en) | Imidazole ring-containing compound and organic electroluminescent element therewith | |
| JP4762514B2 (en) | 3,6-diphenylcarbazole derivative | |
| KR20140064686A (en) | Anthracene derivatives compounds and organic electroluminescent devices comprising the same | |
| JP4411708B2 (en) | Bis (aminostyryl) benzene compound | |
| KR20190129509A (en) | Multicyclic compound and organic light emitting device comprising the same | |
| TW201127782A (en) | Triphenylene based aromatic compounds and OLEDs utilizing the same | |
| TWI428312B (en) | 9,10-bisphenylphenanthrene derivative and organic light emitting diode using the same | |
| JP2004115441A (en) | High-molecular weight perylene derivative, production method therefor, hole transport material and dopant containing the same, and organic el element using the same | |
| JP4576141B2 (en) | Carbazole derivatives containing fluorene groups | |
| CN114853778B (en) | Organic electroluminescent material and application thereof | |
| KR100868303B1 (en) | Diaryl trianthracene derivatives and organic light emitting layer or diode comprising the same | |
| JP5084781B2 (en) | Fluorene compound and organic electroluminescence device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051026 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090304 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090310 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090511 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090602 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090611 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120619 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4327443 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150619 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |