CN103228661A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents
Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDFInfo
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- CN103228661A CN103228661A CN201180055620XA CN201180055620A CN103228661A CN 103228661 A CN103228661 A CN 103228661A CN 201180055620X A CN201180055620X A CN 201180055620XA CN 201180055620 A CN201180055620 A CN 201180055620A CN 103228661 A CN103228661 A CN 103228661A
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- unsubstituted
- replacement
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- alkyl
- aryl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 142
- -1 amine compound Chemical class 0.000 claims description 96
- 239000010410 layer Substances 0.000 claims description 44
- 239000012044 organic layer Substances 0.000 claims description 37
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 34
- 238000005401 electroluminescence Methods 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 125000001072 heteroaryl group Chemical group 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 18
- 229910052805 deuterium Inorganic materials 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- 125000005104 aryl silyl group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000001769 aryl amino group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005580 triphenylene group Chemical group 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 117
- 239000002585 base Substances 0.000 description 96
- 239000000203 mixture Substances 0.000 description 74
- 238000002360 preparation method Methods 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000012153 distilled water Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000001035 drying Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000000284 extract Substances 0.000 description 13
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000005561 phenanthryl group Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical class CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 7
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 125000004076 pyridyl group Chemical group 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 0 CC=C[C@@]([C@](C=*C)c1c2)N(C)c1cc1c2cc(CCCCC2)c2c1 Chemical compound CC=C[C@@]([C@](C=*C)c1c2)N(C)c1cc1c2cc(CCCCC2)c2c1 0.000 description 4
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 229940126086 compound 21 Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 4
- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 description 3
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 3
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 3
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 3
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 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
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000004770 chalcogenides Chemical group 0.000 description 2
- 125000000259 cinnolinyl group Chemical class N1=NC(=CC2=CC=CC=C12)* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 2
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 2
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- BTTNYQZNBZNDOR-UHFFFAOYSA-N 2,4-dichloropyrimidine Chemical compound ClC1=CC=NC(Cl)=N1 BTTNYQZNBZNDOR-UHFFFAOYSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- MBHPOBSZPYEADG-UHFFFAOYSA-N 2-bromo-9,9-dimethylfluorene Chemical class C1=C(Br)C=C2C(C)(C)C3=CC=CC=C3C2=C1 MBHPOBSZPYEADG-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- XZVNKEAPHZSYCJ-UHFFFAOYSA-N 4-[4-amino-4-(4-phenylphenyl)cyclohexa-1,5-dien-1-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=CCC(N)(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 XZVNKEAPHZSYCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- UCFHSBJQHWRYTB-UHFFFAOYSA-N Bc1cccc(-[n]2c3ccc(c4ccccc4[o]4)c4c3c3c2cccc3)c1 Chemical compound Bc1cccc(-[n]2c3ccc(c4ccccc4[o]4)c4c3c3c2cccc3)c1 UCFHSBJQHWRYTB-UHFFFAOYSA-N 0.000 description 1
- RYAJPPAURNCXJQ-UHFFFAOYSA-N C(C1)C=Cc2c1[o]c1c2ccc2c1c1ccccc1[n]2-c1cc(-c2cc3c(cccc4)c4c(cccc4)c4c3cc2)ccc1 Chemical compound C(C1)C=Cc2c1[o]c1c2ccc2c1c1ccccc1[n]2-c1cc(-c2cc3c(cccc4)c4c(cccc4)c4c3cc2)ccc1 RYAJPPAURNCXJQ-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZPVONLLRBPTGCG-UHFFFAOYSA-N [O-][N+](c1ccccc1-c1cccc2c1[o]c1ccccc21)=O Chemical compound [O-][N+](c1ccccc1-c1cccc2c1[o]c1ccccc21)=O ZPVONLLRBPTGCG-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000005382 boronyl group Chemical group 0.000 description 1
- CGCDZBJYFKZTOK-UHFFFAOYSA-N butyl(methyl)phosphane Chemical group CCCCPC CGCDZBJYFKZTOK-UHFFFAOYSA-N 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- ZWJINEZUASEZBH-UHFFFAOYSA-N fenamic acid Chemical compound OC(=O)C1=CC=CC=C1NC1=CC=CC=C1 ZWJINEZUASEZBH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VXPCQISYVPFYRK-UHFFFAOYSA-N profenamine hydrochloride Chemical compound Cl.C1=CC=C2N(CC(C)N(CC)CC)C3=CC=CC=C3SC2=C1 VXPCQISYVPFYRK-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Indole Compounds (AREA)
Abstract
Organic electroluminescent compounds comprising a triphenylene conjugated to a five-ring fused heterocyclic system, as depicted in formula 1 are provided. Also provided is an organic electroluminescent device comprising these compounds. The organic electroluminescent compounds disclosed herein exhibit good luminous efficiency and excellent material life. They can be used to manufacture OLED devices very superior in terms of operating life and which consume less power due to improved power efficiency.
Description
Technical field
The present invention relates to novel organic electroluminescent compounds and the organic electroluminescence device that comprises this compound.
Technical background
In display device, the electroluminescent of self-emission display device (EL) device is preferred, because they provide wide visual angle, excellent contrast gradient and the speed of response fast.Eastman Kodak Co (Eastman Kodak) has at first developed a kind of organic EL device in 1987, this device uses low molecular weight aromatic diamines and aluminium complex as the material [Appl.Phys.Lett.51,913,1987] that forms electroluminescence layer.
The greatest factor of the luminous efficiency of decision Organic Light Emitting Diode (OLED) is an electroluminescent material.Although up to the present fluorescent material has been widely used as electroluminescent material, from electroluminescent mechanism, the exploitation phosphor material is luminous efficiency to be improved to be up to one of preferred approach of 4 times in theory.Up to the present, iridium (III) complex compound is well-known a kind of phosphor material, comprises (acac) Ir (btp)
2, Ir (ppy)
3And Firpic, respectively as redness, green and blue phosphorescent material.Specifically, many phosphor materials are studied in Japan, Europe and the U.S. at present.
At present, known CBP is the substrate material that is widely used as phosphor material most.Reported the efficient OLED that uses the hole blocking layer that comprises BCP, BAlq etc.Pioneer Electronic Corp. (Japan) etc. has reported and has used the high-performance OLED of BAlq derivative as matrix.
Although these materials provide good electroluminescence characters,, may degrade in the high temperature deposition course of processing in a vacuum, thereby be disadvantageous because they have the thermostability of low second-order transition temperature and difference.Because the power efficiency of OLED is determined by (π/voltage) * current efficiency, so power efficiency and voltage are inversely proportional to.Need high power efficiency to reduce the watt consumption of OLED.In fact, use the OLED of phosphor material to provide than the much better current efficiency (cd/A) of OLED of using fluorescent material.But, when current material when for example BAlq, CBP etc. are as the matrix of phosphor material, to compare and use the OLED of fluorescent material not having clear superiority aspect the power efficiency (lm/W), this is because driving voltage is higher.In addition, use life-span of OLED device of this type of material and unsatisfactory, need therefore that development is a kind of to have more high performance more stable substrate material.
Simultaneously, Korean Patent discloses the compound that discloses a kind of electroluminescent organic material 2010-0056490 number, and wherein benzo [9,10] phenanthryl (triphenylene) is by replacements such as carbazole, diphenylene-oxide, dibenzothiophene.Above-mentioned file KR2010-0056490 does not disclose such compound, and wherein benzo [9,10] phenanthryl links to each other with the quinary heteroaryl group, this quinary heteroaryl with comprise that the ring of thionaphthene, indoles, indenes and cumarone condenses at the carbazole place.
Summary of the invention
Technical problem
Therefore, the present invention notices the problem that correlation technique exists, and one object of the present invention is to provide the organic electroluminescent compounds with main chain, thereby can provide better luminous efficiency and the device lifetime with suitable chromaticity coordinates with respect to conventional material.
Another object of the present invention is to provide the organic electroluminescence device with high-level efficiency and long service live, and this luminescent device uses organic electroluminescent compounds as electroluminescent material.
Technical scheme
A kind of compound that is used for the organic electroluminescent compounds that following Chemical formula 1 represents is provided, and the organic electroluminescence device that uses this compound.Because organic electroluminescent compounds of the present invention has superior luminous efficiency and excellent life properties, it can be used for making the OLED device, and this device has extremely superior working life and owing to improved power efficiency consumes less power.
Chemical formula 1
Wherein:
Ring A represents
Ring C represents
Ring B represents
X
1To X
4Represent CR independently
3Or N;
Y
1And Y
2Represent independently singly-bound ,-O-,-S-,-C (R
11) (R
12)-,-Si (R
13) (R
14)-or-N (R
15)-, gets rid of wherein Y
1And Y
2It all is single bonded situation;
R
1To R
3Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted 5-to 7-unit Heterocyclylalkyl, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl Cycloalkylfused with one or more (C3-C30), with replacement or the first Heterocyclylalkyl of unsubstituted one or more aromatic ring condensed 5-to 7-, with replacement or unsubstituted one or more aromatic ring condensed (C3-C30) cycloalkyl,-NR
16R
17,-SiR
18R
19R
20,-SR
21,-OR
22, cyano group, nitro or hydroxyl; Perhaps replacement that they can be by having or do not have condensed ring or unsubstituted (C3-C30) alkenylene or replacement or unsubstituted (C3-C30) alkylidene group link to each other with adjacent substituting group and form alicyclic ring and monocycle or many cyclophanes ring, and the carbon atom of this alicyclic ring and monocycle or many cyclophanes ring can be replaced by one or more heteroatomss that are selected from N, O and S;
R
11To R
22Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl, replacement or unsubstituted 5-to 7-unit's Heterocyclylalkyl or replacement or unsubstituted (C3-C30) cycloalkyl independently; Perhaps replacement that they can be by having or do not have condensed ring or unsubstituted (C3-C30) alkenylene or replacement or unsubstituted (C3-C30) alkylidene group link to each other with adjacent substituting group and form alicyclic ring and monocycle or many cyclophanes ring, and the carbon atom of this alicyclic ring and monocycle or many cyclophanes ring can be replaced by one or more heteroatomss that are selected from N, O and S;
L
1Expression singly-bound, replacement or unsubstituted (C6-C30) arylidene, replacement or unsubstituted (C2-C30) heteroarylidene, replacement or unsubstituted (C3-C30) ring alkylidene group ,-L
2-L
3-or-L
3-L
2-;
L
2Expression replaces or unsubstituted (C6-C30) arylidene;
L
3Expression replaces or unsubstituted (C2-C30) heteroarylidene;
Ar
1And Ar
2Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl independently;
O represents 1 to 4 integer, and when o be during more than or equal to 2 integer, each R
1Can be identical or differ from one another;
P represents 1 or 2 integer, and when p represents 2, each R
2Can be identical or differ from one another; And
Described Heterocyclylalkyl, heteroarylidene and heteroaryl comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P.
Term used herein " alkyl ", " alkoxyl group " and other substituting group that contains " alkyl " part comprise a straight chain and a chain portion, and " cycloalkyl " comprises polynuclear hydrocarbon ring (for example replacing or unsubstituted adamantyl or replacement or unsubstituted (C7-C30) bicyclic alkyl) and monocyclic hydrocarbon ring.Term used herein " aryl " refers to by removing the organic group that hydrogen atom obtains from aromatic hydrocarbon, and it can comprise the monocycle or the condensed ring of 4-to 7-unit, particularly 5-or 6-unit, even also comprises the structure by singly linked a plurality of aryl.Its object lesson includes but not limited to: phenyl, naphthyl, xenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, benzo [9,10] phenanthryl (triphenylenyl), pyrenyl, perylene base (perylenyl),
Base (chrysenyl), naphthacenyl (naphthacenyl), fluoranthene base (fluoranthenyl) etc.Described naphthyl comprises 1-naphthyl and 2-naphthyl, described anthryl comprises 1-anthryl, 2-anthryl and 9-anthryl, described phenanthryl comprises 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, and described naphthacenyl (naphthacenyl) comprises 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl.Described pyrenyl comprises 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, described xenyl comprises 2-xenyl, 3-xenyl and 4-xenyl, described terphenyl comprises right-terphenyl-4-base, right-terphenyl-the 3-base, right-terphenyl-the 2-base ,-terphenyl-4-base ,-terphenyl-3-base and-terphenyl-2-base, described fluorenyl comprises 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
Term used herein " heteroaryl " expression comprise 1-4 be selected from B, N, O, S, P (=O), the heteroatoms of Si and P is as the aromatic ring frame atom, and other aromatic ring frame atoms aromatic yl group that is carbon.It can be 5 yuan of obtaining with one or more phenyl ring condensations or 6 yuan of bicyclic heteroaryls or polyheteroaromatic, and can be fractional saturation.In the present invention, " heteroaryl " comprises one or more heteroaryls by singly linked structure.Described heteroaryl comprises divalent aryl, wherein the heteroatoms in the ring can oxidized or quaternized formation for example N-oxide compound or quaternary ammonium salt.Their object lessons include, but are not limited to, and bicyclic heteroaryl is furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazole base, triazinyl, tetrazine base, triazolyl, furazan base (furazanyl), pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc. for example; Polyheteroaromatic is benzofuryl for example, benzothienyl, isobenzofuran-base, benzimidazolyl-, benzothiazolyl, the benzisothiazole base, benzoisoxazole base benzoxazolyl, pseudoindoyl, indyl, indazolyl, the diazosulfide base, quinolyl, isoquinolyl, cinnolines base (cinnolinyl), quinazolyl, quinoxalinyl (quinoxalinyl), carbazyl, acridyl, phenanthridinyl (phenanthridinyl), phenanthroline base phenoxazinyl, phenazinyl, phenothiazinyl, benzo dioxolyl (benzodioxolyl), dibenzofuran group, dibenzothiophene base etc.; Its N-oxide compound (for example pyridyl N-oxide compound, quinolyl N-oxide compound); Its quaternary ammonium salt etc.
Pyrryl comprises: 1-pyrryl, 2-pyrryl and 3-pyrryl; Pyridyl comprises 2-pyridyl, 3-pyridyl and 4-pyridyl; Indyl comprises 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl and 7-indyl; Pseudoindoyl comprises 1-pseudoindoyl, 2-pseudoindoyl, 3-pseudoindoyl, 4-pseudoindoyl, 5-pseudoindoyl, 6-pseudoindoyl and 7-pseudoindoyl; Furyl comprises 2-furyl and 3-furyl; Benzofuryl comprises 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl and 7-benzofuryl; Isobenzofuran-base comprises 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base and 7-isobenzofuran-base; Quinolyl comprises 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; Isoquinolyl comprises 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl and 8-isoquinolyl; Quinoxalinyl comprises 2-quinoxalinyl, 5-quinoxalinyl and 6-quinoxalinyl; Carbazyl comprises 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl and 9-carbazyl; Phenanthridinyl comprises 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl and 10-phenanthridinyl; Acridyl comprises 1-acridyl, 2-acridyl, 3-acridyl, 4-acridyl and 9-acridyl; The phenanthroline base comprises 1,7-phenanthroline-2-base, 1,7-phenanthroline-3-base, 1,7-phenanthroline-4-base, 1,7-phenanthroline-5-base, 1,7-phenanthroline-6-base, 1,7-phenanthroline-8-base, 1,7-phenanthroline-9-base, 1,7-phenanthroline-10-base, 1,8-phenanthroline-2-base, 1,8-phenanthroline-3-base, 1,8-phenanthroline-4-base, 1,8-phenanthroline-5-base, 1,8-phenanthroline-6-base, 1,8-phenanthroline-7-base, 1,8-phenanthroline-9-base, 1,8-phenanthroline-10-base, 1,9-phenanthroline-2-base, 1,9-phenanthroline-3-base, 1,9-phenanthroline-4-base, 1,9-phenanthroline-5-base, 1,9-phenanthroline-6-base, 1,9-phenanthroline-7-base, 1,9-phenanthroline-8-base, 1,9-phenanthroline-10-base, 1,10-phenanthroline-2-base, 1,10-phenanthroline-3-base, 1,10-phenanthroline-4-base, 1,10-phenanthroline-5-base, 2,9-phenanthroline-1-base, 2,9-phenanthroline-3-base, 2,9-phenanthroline-4-base, 2,9-phenanthroline-5-base, 2,9-phenanthroline-6-base, 2,9-phenanthroline-7-base, 2,9-phenanthroline-8-base, 2,9-phenanthroline-10-base, 2,8-phenanthroline-1-base, 2,8-phenanthroline-3-base, 2,8-phenanthroline-4-base, 2,8-phenanthroline-5-base, 2,8-phenanthroline-6-base, 2,8-phenanthroline-7-base, 2,8-phenanthroline-9-base, 2,8-phenanthroline-10-base, 2,7-phenanthroline-1-base, 2,7-phenanthroline-3-base, 2,7-phenanthroline-4-base, 2,7-phenanthroline-5-base, 2,7-phenanthroline-6-base, 2,7-phenanthroline-8-base, 2,7-phenanthroline-9-base and 2,7-phenanthroline-10-base; Phenazinyl comprises 1-phenazinyl and 2-phenazinyl; Phenothiazinyl comprises 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl and lysivane base; Phenoxazinyl comprises 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl and 10-phenoxazinyl; Oxazolyl comprises 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; Oxadiazole comprises 2-oxadiazole base and 5-oxadiazole base; The furazan base comprises 3-furazan base; Dibenzofuran group comprises 1-dibenzofuran group, 2-dibenzofuran group, 3-dibenzofuran group and 4-dibenzofuran group; The dibenzothiophene base comprises 1-dibenzothiophene base, 2-dibenzothiophene base, 3-dibenzothiophene base and 4-dibenzothiophene base.
Term used herein " (C1-C30) alkyl " comprises (C1-C20) alkyl or (C1-C10) alkyl, and term " (C6-C30) aryl " comprises (C6-C20) aryl.Term " (C2-C30) heteroaryl " comprises (C2-C20) heteroaryl, and term " (C3-C30) cycloalkyl " comprises (C3-C20) cycloalkyl or (C3-C7) cycloalkyl.Term " (C2-C30) alkenyl or alkynyl " comprises (C2-C20) alkenyl or alkynyl, perhaps (C2-C10) alkenyl or alkynyl.
In statement used herein " replacement or unsubstituted " (perhaps " having or do not have substituting group "), the unsubstituted substituting group of term " (the having substituting group) of replacement " expression further is substituted base and replaces.R
1To R
3, L
1, L
2, L
3, Ar
1, Ar
2And R
11To R
22Each substituting group can also be replaced by one or more substituting groups that are selected from down group: deuterium, halogen, (C1-C30) alkyl, (C1-C30) alkyl that halogen replaces, (C6-C30) aryl, (C2-C30) heteroaryl, (C6-C30) (C2-C30) heteroaryl of alkyl replacement, (C6-C30) (C2-C30) heteroaryl of aryl replacement, (C3-C30) cycloalkyl, 5-to 7-unit Heterocyclylalkyl, three (C1-C30) alkyl silyl, three (C6-C30) aryl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, the N-carbazyl, two (C1-C30) alkylamino, two (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, two (C6-C30) aryl boryl (boronyl), two (C1-C30) alkyl boryl, (C1-C30) alkyl (C6-C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carboxyl, nitro and hydroxyl.
In addition, Chemical formula 1
Can be selected from following structure, but be not limited thereto:
Wherein, R
1, R
2, R
11To R
15, o and p definition identical with the definition in the Chemical formula 1.
Particularly, X
1To X
4Represent N or CR independently
3Y
1And Y
2Represent independently singly-bound ,-O-,-S-,-C (R
11R
12)-or-N (R
15)-, gets rid of wherein Y
1And Y
2It all is single bonded situation; L
1Expression singly-bound, phenylene, naphthalene, biphenylene, 9,9-phenylbenzene fluorenylidene, 9,9-dimethyl fluorenylidene, dibenzothiophene, diphenylene-oxide or spiral shell fluorenes; Ar
1And Ar
2Represent hydrogen, phenyl, xenyl, naphthyl, 9 independently, 9-dibenzo fluorenyl, 9,9-dimethyl fluorenyl, fluoranthene base (fluoranthenyl), pyridyl, N-phenyl carbazole base, dibenzothiophene or diphenylene-oxide, and Ar
1And Ar
2Phenyl, xenyl, naphthyl, 9,9-dibenzo fluorenyl, 9,9-dimethyl fluorenyl, fluoranthene base, pyridyl, N-phenyl carbazole base, dibenzothiophene and diphenylene-oxide can also be replaced by one or more substituting groups that are selected from down group: deuterium, fluorine, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, triphenyl silyl, trimethyl silyl, diphenyl methyl silyl, phenyl and naphthyl; R
1To R
3Represent hydrogen, deuterium, phenyl, pyridyl, dibenzofuran group, dibenzothiophene base, triphenyl silyl or diphenyl methyl silyl independently; R
11To R
22Represent hydrogen, deuterium, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, trifluoromethyl, phenyl, naphthyl, pyridyl or quinolyl independently, perhaps replacement that they can be by having or do not have condensed ring or unsubstituted (C3-C7) alkenylene or replacement or unsubstituted (C3-C7) alkylidene group connect forming condensed ring, and R
11To R
22Phenyl also can be replaced by one or more substituting groups that are selected from down group: deuterium, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, trifluoromethyl, phenyl and naphthyl.
Organic electroluminescent compounds of the present invention can be enumerated as following compound, but they are not construed as limiting the present invention:
Can shown in (for example) following scheme 1, prepare organic electroluminescent compounds of the present invention, but be not limited thereto.
[scheme 1]
In scheme 1, ring A, ring B, ring C, L
1, Ar
1, Ar
2, R
1Identical with the definition of o with the definition in the Chemical formula 1; X represents halogen.
A kind of organic electroluminescence device is provided, and it comprises first electrode; Second electrode; And one or more layers organic layer between described first electrode of insertion and second electrode, wherein said organic layer comprises one or more organic electroluminescent compounds of being represented by Chemical formula 1.Described organic layer comprises electroluminescence layer, and the organic electroluminescent compounds of Chemical formula 1 can be used as the matrix in the described electroluminescence layer.In addition, can after adding other substrate material, use the compound of Chemical formula 1.
In electroluminescence layer, when the organic electroluminescent compounds of Chemical formula 1 is used as matrix, comprise one or more phosphorescent dopants.Be used for the not concrete restriction of phosphorescent dopants of organic electroluminescence device of the present invention, but optional from the represented compound of following Chemical formula 2:
Chemical formula 2
M
1L
101L
102L
103
Wherein:
M
1Be the metal that is selected from the periodic table of elements the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 13rd family, the 14th family, the 15th family and the 16th family, ligand L
101, L
102, and L
103Be independently selected from following structure:
R
201To R
203Represent that independently hydrogen, deuterium, halogen replacement or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl or halogen;
R
204To R
219Represent hydrogen independently, deuterium, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C1-C30) alkoxyl group, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted (C2-C30) thiazolinyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted list-(C1-C30) alkylamino or replacement or unsubstituted two-(C1-C30) alkylaminos, replace or unsubstituted list-(C6-C30) arylamino or replacement or unsubstituted two-(C6-C30) arylaminos, SF
5, replacement or unsubstituted three (C1-C30) alkyl silyl, replacement or unsubstituted two (C1-C30) alkyl (C6-C30) aryl silyl, replacement or unsubstituted three (C6-C30) aryl silyl, cyano group or halogen;
R
220To R
223Represent independently that hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl;
R
224And R
225Represent hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen, perhaps R independently
224And R
225(C3-C12) alkenylene that can be by having or do not have condensed ring or (C3-C12) alkylidene group be connected to form alicyclic ring and monocycle or many cyclophanes ring;
R
226Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl or halogen;
R
227To R
229Represent hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen independently; And
Q represents
Or
R
231To R
242Represent that independently hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxyl group, halogen, replacement or unsubstituted (C6-C30) aryl, cyano group or replacement or unsubstituted (C3-C30) cycloalkyl, perhaps they can be connected to form volution or condensed ring by alkylidene group or alkenylene and adjacent substituting group, perhaps can pass through alkylidene group or alkenylene and R
207Or R
208Be connected to form saturated or unsaturated condensed ring.
The dopant compound of Chemical formula 2 can be enumerated as following compound, but is not limited thereto:
In organic electronic devices of the present invention, except the represented organic electroluminescent compounds of Chemical formula 1, described organic layer can comprise simultaneously that also one or more are selected from the compound of aromatic amine compound and styryl aromatic amine compound.The example of described aromatic amine compound or styryl aromatic amine compound is referring to korean patent application 10-2008-0123276,10-2008-0107606 or 10-2008-0118428 number, but is not limited thereto.
In addition, in organic electroluminescence device of the present invention, except the represented organic electroluminescent compounds of Chemical formula 1, described organic layer can comprise that also one or more are selected from the metal or the complex compound of the organo-metallic of the periodic table of elements the 1st family, the 2nd family, period 4 and period 5 transition metal, lanthanide series metal and d-transition element.Described organic layer can comprise electroluminescence layer and charge generation layer.
In addition, except the organic electroluminescent compounds that described Chemical formula 1 is represented, described organic layer also can comprise the organic electro luminescent layer of one or more emission blue light, green glow or ruddiness simultaneously, to realize the organic electroluminescence device of emission white light.The example of the compound of blue light-emitting, green glow or ruddiness can be korean patent application 10-2008-0123276,10-2008-0107606 or 10-2008-0118428 number described compound, but is not limited thereto.
In organic electroluminescence device of the present invention, the layer (hereinafter referred to as " upper layer ") that is selected from chalcogenide layer, metal halide and metal oxide layer can be placed on the internal surface of one or two electrode in the electrode pair.More particularly, the metal chalcogenide of silicon or aluminium (comprising oxide compound) layer can place on the anode surface of electroluminescent medium layer, and metal halide or metal oxide layer can place on the cathode surface of described electroluminescent medium layer.Thereby obtain job stability.For example, chalkogenide can be SiO
x(1≤x≤2), AlO
x(1≤x≤1.5), SiON, SiAlON etc.For example, metal halide can be LiF, MgF
2, CaF
2, rare earth metal fluorochemical etc.For example, metal oxide can be Cs
2O, Li
2O, MgO, SrO, BaO, CaO etc.
In organic electroluminescence device of the present invention, the mixing zone of electric transmission compound and reductibility doping agent also preferably is set, perhaps the mixing zone of hole transport compound and oxidisability doping agent at least one surface of prepared electrode pair.In this case, because the electric transmission compound is reduced into negatively charged ion, thereby promotes electronics to inject and be transferred to electroluminescent medium from the mixing zone.In addition, because the oxidized formation positively charged ion of hole transport compound, thereby promote the hole to inject and be transferred to electroluminescent medium from the mixing zone.Preferred oxidisability doping agent comprises various Lewis acids and acceptor compound.Preferred reductibility doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and composition thereof.In addition, the electroluminescent device that emits white light with two-layer or more multi-layered electroluminescence layer can use the reductibility dopant layer to prepare as charge generation layer.
Useful effect of the present invention
According to the present invention, organic electroluminescent compounds can have high-luminous-efficiency and can have excellent material lifetime, can be used for preparing the OLED device with extremely superior working life.
The embodiment of invention
Be example hereinafter, the electroluminescent character of organic electroluminescent compounds of the present invention, its preparation method and this device is described further with representative compounds of the present invention.But these embodiment only are used to the embodiment purpose is described, are not intended to limit the scope of the invention.
[preparation example 1] preparation compound 1
The preparation of compound 1-1
Under 100 ℃, to 2-iodobenzene (30 grams, 120.4 mmoles), 4-bromophenyl boric acid (26 grams, 132.5 mmoles), Pd (PPh
3)
4(6.9 grams, 6.02 mmoles), 150 milliliters of 2M Na
2CO
3Heat with 500 milliliters of toluene.After 4 hours, this mixture is cooled to room temperature,, washs, use anhydrous MgSO with distilled water with ethyl acetate (EA) extraction
4Carry out drying, under reduced pressure, distill, and carry out post and separate, obtain compound 1-1 (28 grams, 100.68 mmoles, 83,33%).
The preparation of compound 1-2
Compound 1-1 (28 grams, 100.68 mmoles) is mixed with 300 milliliters of triethyl-phosphites, and stirred 6 hours down at 150 ℃.This mixture is cooled to room temperature, under reduced pressure, distills,, wash with distilled water again with the EA extraction.Subsequently, use anhydrous MgSO
4Carry out drying, under reduced pressure, distill, carry out post again and separate, obtain compound 1-2 (11 grams, 44.69 mmoles, 44.38%).
The preparation of compound 1-3
With compound 1-2 (30 grams, 101.29 mmoles), iodobenzene (41.3 grams, 202.59 mmoles), CuI (9.6 grams, 50.64 mmoles), Cs
2CO
3(82.5 grams, 253.2 mmoles) and 600 milliliters of toluene mix, and heat under 50 ℃, add quadrol (6.8 milliliters, 101.29 mmoles).Under refluxing, this mixture is stirred.After 14 hours, this mixture is cooled to room temperature, and to wherein adding distilled water.With EA this mixture is extracted, use anhydrous MgSO
4Carry out drying, under reduced pressure, distill, and carry out post and separate, obtain compound 1-3 (32 grams, 85.96 mmoles, 84.86%).
The preparation of compound 1-4
Compound 1-3 (32 grams, 85.96 mmoles) is dissolved among 300 milliliters of THF, and slowly adds n-Butyl Lithium (37.8 milliliters, 94.55 mmoles, the hexane solution of 2.5M) down at-78 ℃.After 1 hour, add trimethyl borate (12.4 milliliters, 111.7 mmoles).At room temperature this mixture was stirred 12 hours, add distilled water again.With EA this mixture is extracted, use anhydrous MgSO
4Carry out drying, under reduced pressure, distill, and carry out post and separate, obtain compound 1-4 (20 grams, 59.31 mmoles, 69.00%).
The preparation of compound 1-5
With compound 1-4 (20 grams, 59.31 mmoles), 1-bromo-2-oil of mirbane (14.3 grams, 71.17 mmoles), Pd (PPh
3)
4(2.7 grams, 2.37 mmoles), 75 milliliters of 2M Na
2CO
3, 300 milliliters of toluene and 70 milliliters of ethanol mix, under refluxing, stir.After 5 hours, this mixture is cooled to room temperature, and to wherein adding distilled water.With EA this mixture is extracted, use anhydrous MgSO
4Carry out drying, under reduced pressure, distill, and carry out post and separate, obtain compound 1-5 (20 grams, 48.25 mmoles, 81.36%).
The preparation of compound 1-6
Compound 1-5 (20 grams, 48.25 mmoles) and 200 milliliters of triethyl-phosphites are mixed, stirred 6 hours down, be cooled to room temperature, and under reduced pressure, distill at 150 ℃.With EA this mixture is extracted, wash, use anhydrous MgSO with distilled water
4Carry out drying, under reduced pressure, distill, and carry out post and separate, obtain compound 1-6 (7 grams, 18.30 mmoles, 37.93%).
The preparation of compound 1-7
In 1 liter two neck round-bottomed flasks (RBF), add compound 1-6 (19.3 grams, 0.058 mole), 1,3-dibromobenzene (82 grams, 0.349 mole), CuI (5.5 grams, 2.91 mmoles), K
3PO
4(25 grams, 0.11 mole), quadrol (4 milliliters, 0.058 mole) and 500 milliliters of toluene, and be heated to 75 ℃.This mixture was stirred 12 hours, remove by filter Cu, use distilled water wash, extract the anhydrous MgSO of organic layer with EA
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 1-7 (20.0 grams, 71%).
The preparation of compound 1-8
Compound 1-7 (20.0 grams, 0.041 mole) is inserted among 1 liter of RBF, vacuum-drying, and add nitrogen.Add 300 milliliters of THF, mixture is cooled to-78 ℃.Slowly just adding-BuLi (2.5M) (24.7 milliliters, 0.061 mole), at low temperatures this mixture was being stirred 1 hour.Add B (i-pro) down at-78 ℃
3(14.2 milliliters, 0.061 mmole) stir this mixture 12 hours.Behind the reaction terminating, add 1M HCl.After 10 minutes, this mixture is washed, extract, the anhydrous MgSO of organic layer with EA with distilled water
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 1-8 (17.7 grams, 90%).
The preparation of compound 1
With 2-bromo benzo [9,10] phenanthryl (7.2 grams, 23.44 mmoles), compound 1-8 (15.9 grams, 35.16 mmoles), Pd (OAc)
2(790 milligrams, 3.51 mmoles), P (t-Bu)
3(4.7 milliliters, 7.03 mmoles), K
3PO
4(2M) (46 milliliters, 93.76 mmoles), 46 milliliters of ethanol and 200 milliliters of toluene add among 500 milliliter of two neck RBF, with this mixture heating up to 120 ℃, and stir 2 hours.Behind the reaction terminating, this mixture is washed, extract, the anhydrous MgSO of organic layer with EA with distilled water
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 1 (6.5 grams, 44%).
The measured value 635 of MS/FAB, theoretical value 634.77
[preparation example 2] preparation compound 10
The preparation of compound 2-1
With dibenzo [b, d] thiophene-4-ylboronic acid (10 grams, 43.84 mmoles), bromo nitryl benzene (8.85 grams, 43.84 mmoles), 70 milliliters of 2M Na
2CO
3The aqueous solution, 200 milliliters of toluene and 70 milliliters of ethanol mix, and stir under refluxing.After 5 hours, this mixture is cooled to room temperature,, washs, use anhydrous MgSO with distilled water with the EA extraction
4Carry out drying, and under reduced pressure, distill.Subsequently, carry out post and separate, obtain compound 2-1 (10 grams, 32.74 mmoles, 74.68%).
The preparation of compound 2-2
Compound 2-1 (10 grams, 32.74 mmoles) is mixed with 100 milliliters of triethyl-phosphites, and stirred 7 hours down at 150 ℃.This mixture is cooled to room temperature, and under reduced pressure, distills.Subsequently, use EA to carry out recrystallization, obtain compound 2-2 (7 grams, 25.60 mmoles, 78.19%).
The preparation of compound 2-3
Prepare compound 2-3 (8.2 grams, 19.1 mmoles, 75%) by the method identical with preparing compound 1-7.
The preparation of compound 2-4
Prepare compound 2-4 (4.7 grams, 12.0 mmoles, 62%) by the method identical with preparing compound 1-8.
The preparation of compound 10
Prepare compound 10 (5.3 grams, 9.2 mmoles, 67%) by the method identical with preparing compound 1.
The measured value 576 of MS/FAB, theoretical value 575.72
[preparation example 3] preparation compound 19
The preparation of compound 3-1
2-(phenyl amino) phenylformic acid (50 grams, 0.23 mole) is dissolved among 1 liter of MeOH, inserts in the ice bath, stirred 10 minutes down at 0 ℃ again.Slowly add SOCl down at 0 ℃
2(60 milliliters, 0.58 mole), 90 ℃ and reflux under this mixture was stirred 12 hours.Behind the reaction terminating, this mixture is washed, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-1 (47 grams, 92%) as photographic developer.
The preparation of compound 3-2
Compound 3-1 (90 grams, 0.3 mole) is added 1.5 liters of THF, slowly add MeMgBr (3.0M) (462 milliliters, 1.38 moles), then this mixture was at room temperature stirred 12 hours.Behind the reaction terminating, this mixture is neutralized, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-2 (80 grams, 90%) as photographic developer.
The preparation of compound 3-3
Compound 3-2 (80 grams, 0.35 mole) is added 1.7 liters of H
3PO
4In, this mixture was at room temperature stirred 12 hours.Behind the reaction terminating, this mixture is neutralized, wash the solid and the filtration of acquisition with water with distilled water.This solid is dissolved in the methylene dichloride, extracts, and neutralize with NaOH.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use hexane to carry out recrystallization, obtain compound 3-3 (64 grams, 87%).
The preparation of compound 3-4
With compound 3-3 (64 grams, 0.30 mole), bromobenzene (52.8 grams, 0.33 mole), Pd (OAc)
2(1.37 grams, 6.11 mmoles), P (t-Bu)
350% (7.3 milliliters, 15.28 mmoles) and NaOt-Bu (58 grams, 0.61 mole) are dissolved in 1.2 liters of toluene, and stir 12 hours down at 120 ℃.Behind the reaction terminating, this mixture is neutralized, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-4 (71 grams, 81%) as photographic developer.
The preparation of compound 3-5
Compound 3-4 (20 grams, 0.07 mole) is dissolved among 800 milliliters of DMF, stirred 10 minutes down at 0 ℃.Slowly add the DMF solution of 350 milliliters of NBS (12.5 grams, 0.07 mole), and this mixture was stirred 6 hours down at 0 ℃.Behind the reaction terminating, this mixture is neutralized, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-5 (21 grams, 84%) as photographic developer.
The preparation of compound 3-6
With compound 3-5 (20 grams, 0.054 mole), 2-chloroaniline (8.4 grams, 0.065 mole), Pd (OAc)
2(370 milligrams, 1.64 mmoles), P (t-Bu)
350% (3.6 milliliters, 5.49 mmoles) and Cs
2CO
3(35.7 grams, 0.109 mole) is dissolved in 300 milliliters of toluene, and stirs 4 hours down at 120 ℃.Behind the reaction terminating, this mixture is neutralized, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-6 (13.6 grams, 60%) as photographic developer.
The preparation of compound 3-7
With compound 3-6 (12.6 grams, 0.03 mole), Pd (OAc)
2(1.37 milligrams, 6.13 mmoles), Tetrafluoroboric acid two-tertiary butyl (methyl) Phosphonium (3 grams, 12.26 mmoles) and Cs
2CO
3(50 grams, 0.15 mole) is dissolved among 240 milliliters of DMA, and stirs 4 hours down at 190 ℃.Behind the reaction terminating, this mixture is neutralized, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, use EA to carry out the column chromatography purifying, obtain compound 3-7 (7 grams, 18.7 mmoles, 70%) as photographic developer.
The preparation of compound 3-8
Prepare compound 3-8 (5.8 grams, 11.0 mmoles, 59%) by the method identical with preparing compound 1-7.
The preparation of compound 3-9
Prepare compound 3-9 (3.6 grams, 7.3 mmoles, 67%) by the method identical with preparing compound 1-8.
The preparation of compound 19
Prepare compound 19 (5.0 grams, 9.2 mmoles, 69%) by the method identical with preparing compound 1.
The measured value 677 of MS/FAB, theoretical value 676.84
[preparation example 4] preparation compound 20
The preparation of compound 4-1
With 1-bromo-2-oil of mirbane (16 grams, 74.25 mmoles), dibenzo [b, d] furans-2-ylboronic acid (23 grams, 96.60 mmoles), Pd (PPh
3)
4(4.2 grams, 3.63 mmoles), 111 milliliters of 2M K
2CO
3The aqueous solution, 100 milliliters of EtOH and 200 milliliters of toluene mix, and are heated to 120 ℃ again and stir simultaneously 3 hours.Behind the reaction terminating, this mixture is washed, this mixture is extracted with EA with distilled water.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, carry out the column chromatography purifying, obtain compound 4-1 (22 grams, 95%).
The preparation of compound 4-2
With compound 4-1 (24 gram, 76.10 mmoles), 200 milliliters of triethyl-phosphites and 200 milliliter 1, the 2-dichlorobenzene mixes, and with this mixture heating up to 180 ℃, stirs 12 hours.Behind the reaction terminating, use water distilling apparatus with unreacted triethyl-phosphite and 1, the 2-dichlorobenzene is removed, and with distilled water mixture is washed, and extracts with EA.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, carry out the column chromatography purifying, obtain compound 4-2 (7 grams, 27.2 mmoles, 33%).
The preparation of compound 4-3
Prepare compound 4-3 (8.4 grams, 20.4 mmoles, 75%) by the method identical with preparing compound 1-7.
The preparation of compound 4-4
Prepare compound 4-4 (4.3 grams, 11.4 mmoles, 56%) by the method identical with preparing compound 1-8.
The preparation of compound 20
Prepare compound 20 (2.8 grams, 5.0 mmoles, 42%) by the method identical with preparing compound 1.
The measured value 560 of MS/FAB, theoretical value 559.65
[preparation example 5] preparation compound 11
The preparation of compound 5-1
With 1-bromo-2-oil of mirbane (39 grams, 0.19 mole), dibenzo [b, d] furans-4-ylboronic acid (45 grams, 0.21 mole), Pd (PPh
3)
4(11.1 grams, 0.0096 mole), 290 milliliters of 2M K
2CO
3The aqueous solution, 290 milliliters of EtOH and 580 milliliters of toluene mix, and are heated to 120 ℃ again and stir simultaneously 4 hours.Behind the reaction terminating, this mixture is washed, extract, the anhydrous MgSO of organic layer with EA with distilled water
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out the column chromatography purifying, obtain compound 5-1 (47 grams, 85%).
The preparation of compound 5-2
With compound 5-1 (47 gram, 0.16 mole), 600 milliliters of triethyl-phosphites and 300 milliliter 1, the 2-dichlorobenzene mixes, and with this mixture heating up to 150 ℃, stirs 12 hours.Behind the reaction terminating, use water distilling apparatus with unreacted triethyl-phosphite and 1, the 2-dichlorobenzene is removed, and with distilled water mixture is washed, and extracts with EA.Use anhydrous MgSO
4Dry organic layer uses rotatory evaporator to remove and desolvates.Subsequently, carry out the column chromatography purifying, obtain compound 5-2 (39 grams, 81%).
The preparation of compound 5-3
In 1 liter two neck RBF, add compound 5-2 (15 grams, 0.058 mole), 1,3-dibromobenzene (82 grams, 0.349 mole), CuI (5.5 grams, 2.91 mmoles), K
3PO
4(25 grams, 0.11 mole), quadrol (4 milliliters, 0.058 mole) and 500 milliliters of toluene, and be heated to 75 ℃.This mixture was stirred 12 hours, filter then, remove Cu.With distilled water this mixture is washed, extract, the anhydrous MgSO of organic layer with EA
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 5-3 (17.1 grams, 71%).
The preparation of compound 5-4
Compound 5-3 (17 grams, 0.041 mole) is inserted among 1 liter of RBF, vacuum-drying, and add nitrogen.Add 300 milliliters of THF, mixture is cooled to-78 ℃.Slowly just adding-BuLi (2.5M) (24.7 milliliters, 0.061 mole), at low temperatures this mixture was being stirred 1 hour.Add B (i-pro) down at-78 ℃
3(14.2 milliliters, 0.061 mmole) stir this mixture 12 hours.Behind the reaction terminating, add 1M HCl.After 10 minutes, this mixture is washed, extract, the anhydrous MgSO of organic layer with EA with distilled water
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 5-4 (13.8 grams, 90%).
The preparation of compound 11
With 2-bromo benzo [9,10] phenanthryl (7.2 grams, 23.44 mmoles), compound 5-4 (13.2 grams, 5.16 mmoles), Pd (OAc)
2(790 milligrams, 3.51 mmoles), P (t-Bu) 3 (4.7 milliliters, 7.03 mmoles), K
3PO
4(2M) (46 milliliters, 93.76 mmoles), 46 milliliters of ethanol and 200 milliliters of toluene add among 500 milliliter of two neck RBF, with this mixture heating up to 120 ℃, and stir 2 hours.Behind the reaction terminating, this mixture is washed, extract, the anhydrous MgSO of organic layer with EA with distilled water
4Carry out drying, use Rotary Evaporators to remove then and desolvate.Subsequently, carry out column purification, obtain compound 11 (5.8 grams, 44%).
The measured value 559 of MS/FAB, theoretical value 559.19
[preparation example 6] preparation compound 21
The preparation of compound 6-1
With 2-bromo-9,9-dimethyl-9H-fluorenes (80 grams, 291 mmoles), 2-chloro aminobenzen (45 milliliters, 437 mmoles), Pd (OAc)
2(2.6 grams, 12 mmoles), P (t-Bu)
3(12 milliliters, 24 mmoles), NaOt-Bu (70 gram, 728 mmoles) and 800 milliliters of toluene mix, and reheat to 120 ℃ stirred 9 hours simultaneously.Behind the reaction terminating, this mixture is cooled to room temperature, extracts, the organic layer that obtains is washed with 400 ml distilled waters with 1.5 liters of EA.Under reduced pressure, remove and desolvate, the solid that obtains is washed, filter and drying with hexane.Subsequently, carry out silica gel column chromatography and recrystallization, obtain compound 6-1 (70 grams, 75%).
The preparation of compound 6-2
With compound 6-1 (70 grams, 218 mmoles), Pd (OAc)
2(2.4 grams, 11 mmoles), PCy
3HBF
4(8 grams, 22 mmoles), Na
2CO
3(70 grams, 654 mmoles) and 1.2 liters of DMA mix, and stir 3 hours down at 190 ℃.Behind the reaction terminating, this mixture is extracted, the organic layer that obtains is washed, use anhydrous MgSO with 200 milliliters distilled water with 1 liter of EA
4Drying is removed organic solvent under reduced pressure.Use silica gel column chromatography to separate and recrystallization to the solid that obtains, obtain compound 6-2 (22 grams, 36%).
The preparation of compound 6-3
With compound 6-2 (15 grams, 53 mmoles), 1,3-dibromobenzene (32 milliliters, 265 mmoles), Pd (OAc)
2(1.2 grams, 5 mmoles), P (t-Bu) 3 (30 milliliters, 64 mmoles), NaOt-Bu (25 grams, 265 mmoles) and 300 milliliters of toluene mix, and stir 24 hours down at 120 ℃.Behind the reaction terminating, this mixture is cooled to room temperature, extracts, the organic layer that obtains is washed with 400 ml distilled waters with 1.5 liters of EA.Subsequently, under reduced pressure, remove and desolvate, the solid that obtains is washed, filter and drying with hexane.Carry out silica gel column chromatography and recrystallization, obtain compound 6-3 (7 grams, 30%).
The preparation of compound 6-4
Compound 6-3 (7 grams, 16 mmoles) is dissolved among 100 milliliters of THF, is just adding-BuLi (hexane solution of 2.5M) (10 milliliters, 24 mmoles) down at-78 ℃.This mixture was stirred 1 hour down at-78 ℃, add B (Oi-Pr)
3(6 milliliters, 24 mmoles).Stirred 2 hours, and stopped this reaction with 20 milliliters of aqueous ammonium chloride solutions.With 500 milliliters of EA extraction gained mixtures, the organic layer that obtains is washed with 200 ml distilled waters.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.With recrystallization the solid that obtains is separated, obtain compound 6-4 (5 grams, 75%).
The preparation of compound 21
With compound 6-4 (3.7 grams, 9.2 mmoles), 2-bromo benzo [9,10] phenanthryl (2.6 grams, 8.3 mmoles), Pd (OAc)
2(94 milligrams, 0.4 mmole), P (t-Bu)
3(0.4 milliliter, 0.8 mmole), Cs
2CO
3(8.2 gram, 25 mmoles), 30 milliliters of toluene, 15 milliliters of EtOH and 15 ml distilled waters mix, 120 ℃ under with this mixture stirring 16 hours.This mixture is cooled to room temperature, and extracts, the organic layer that obtains is washed, under reduced pressure, remove organic solvent then with 50 ml distilled waters with 200 milliliters of EA.With hexane the solid that obtains is washed, filter again dry.Use silica gel column chromatography to separate and recrystallization to the solid that obtains, obtain compound 21 (1.1 grams, 22%).
The measured value 585 of MS/FAB, theoretical value 585.25
[preparation example 7] preparation compound 28
The preparation of compound 7-1
2-bromo benzo [9,10] phenanthryl (63.7,207.4 mmole) is dissolved among 1.5 liters of THF, and is cooled to-78 ℃.After 10 minutes, slowly just adding-BuLi (hexane solution of 2.5M) (125 milliliters, 311 mmoles), this mixture was being stirred 1 hour.Slowly add triethyl borate (67 milliliters, 311 mmoles), this mixture was stirred 24 hours.Behind the reaction terminating, add 1M HCl, this mixture is extracted with EA.Subsequently, use anhydrous MgSO
4Remove residual water-content, carry out drying then, and from hexane recrystallization, obtain compound 7-1 (31.8 gram, 55%).
The preparation of compound 7-2
With 2,4-dichloro pyrimidine (9.7 grams, 65.1 mmoles), compound 7-1 (17.72 grams, 65.1 mmoles), Pd (PPh
3)
4(3.76 grams, 3.25 mmoles), Na
2CO
3(20.7 grams, 195.3 mmoles) and 1.5 liters of DME insert in the flask and dissolving, under 120 ℃ this mixture are stirred 7 hours.After the reaction, stop this reaction, obtain organic layer, use anhydrous MgSO by using the EA extraction thereby slowly add distilled water
4Remove residual water-content.Subsequently, carry out drying and separate, obtain compound 7-2 (4 grams, 20%) with post.
The preparation of compound 28
In flask, be dissolved among 100 milliliters of DMF NaH (651 grams, 19.3 mmoles) and stirring.In this NaH solution, add the DMF solution of compound 5-2 (4 grams, 15.4 mmoles), this mixture is stirred 1 hour (reaction mixture A).Compound 7-2 (4.4 grams, 12.9 mmoles) is dissolved among the DMF, stirs, and it is added among the reaction mixture A that has stirred 1 hour, at ambient temperature mixture was stirred 24 hours again.Behind the reaction terminating, filter the gained solid,, use the column chromatography purifying, obtain compound 28 (3.5 grams, 48%) with the EA washing.
The measured value 561 of MS/FAB, theoretical value 561.18
[embodiment 1] uses organic electroluminescent compounds of the present invention to prepare the OLED device
Use the compound that is used for organic electronic material of the present invention to make the OLED device.At first, (15 Ω/) (available from SCP company (Samsung-Corning)) carry out ultrasonic cleaning with trieline, acetone, ethanol and distilled water to the transparency electrode ito thin film that is used for OLED successively that will be made by glass, are stored in the Virahol before using.Then, the ITO substrate is contained in the substrate folder (folder) of vacuum sediment equipment, 2-TNATA[4,4 '; 4 "-three (N, N-(2-naphthyl)-phenyl amino) triphenylamine] place the cell (cell) of vacuum sediment equipment, be vented to indoor vacuum tightness then and be up to 10
-6Holder.Then, apply electric current to described cell and make its evaporation, thereby deposit thickness is the hole injection layer of 60 nanometers on the ITO substrate.Subsequently, with N, N '-two (4-xenyl)-N, N '-two (4-xenyl)-4,4 '-benzidine base places another cell of vacuum sediment equipment, by applying electric current to this cell so that NPB evaporation, thereby deposit thickness is the hole transmission layer of 20 nanometers on described hole injection layer.After forming hole injection layer and hole transmission layer, form electroluminescence layer in the above, specific as follows.In vacuum vapor deposition equipment, will place a cell as the compound 10 of matrix, with 11-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-12-phenyl-11,12-indoline [2,3-a] carbazole places another cell.These two kinds of materials are evaporated with identical speed, and as matrix.Add doping agent D-5 and make that matrix is that 15 weight % are adulterated, thereby vapour deposition thickness is the electroluminescence layer of 30 nanometers on described hole transmission layer.Subsequently, vapour deposition thickness is Alq[three (the oxine)-aluminium (III) of 20 nanometers on described electroluminescence layer] as electron transfer layer.Then, vapour deposition thickness be the Liq (quinoline closes lithium) of 2 nanometers as electron injecting layer, using another vacuum vapor deposition equipment to come vapour deposition thickness then is the Al negative electrode of 150 nanometers, thereby makes OLED.
Before use, each compound that is used for the OLED device passes through 10
-6Holder vacuum-sublimation down is able to purifying.
The result is that it is 1.6 milliamperes/centimetre that confirmation electric current under the voltage of 4.7V flows
2, and emission 685cd/m
2Green glow.
[embodiment 2] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use the method identical with embodiment 1 to make the OLED device, difference is, uses compound 11 as substrate material in electroluminescence layer, and use D-34 is as doping agent.
The result is that it is 5.3 milliamperes/centimetre that confirmation electric current under the voltage of 5.6V flows
2, and emission 2190cd/m
2Green glow.
[embodiment 3] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use the method identical with embodiment 1 to make the OLED device, difference is, uses compound 21 as substrate material in electroluminescence layer, and use D-34 is as doping agent.
The result is that it is 3.0 milliamperes/centimetre that confirmation electric current under the voltage of 5.2V flows
2, and emission 1240cd/m
2Green glow.
[embodiment 4] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use the method identical with embodiment 1 to make the OLED device, difference is, in electroluminescence layer separately use compound 28 as substrate material.
The result is that it is 10.6 milliamperes/centimetre that confirmation electric current under the voltage of 6.4V flows
2, and emission 4520cd/m
2Green glow.
The electroluminescent character of the OLED device of the electroluminescent material of [comparative example 1] use prior art
Make the OLED device by the method identical with embodiment 1, difference is, use CBP (4,4 '-two (carbazole-9-yl) xenyl) obtain electroluminescence layer as doping agent by vapour deposition as matrix and Compound D-4, using the vapour deposition between described electroluminescence layer and electron transfer layer of two (2-methyl-oxine closes (quinolinato)) 4-phenylphenol aluminium (III) to obtain thickness is the hole blocking layer of 10 nanometers.
The result is that it is 3.8 milliamperes/centimetre that confirmation electric current under the voltage of 7.5V flows
2, and emission 1000cd/m
2Green glow.
Use organic electroluminescent compounds of the present invention can show excellent electroluminescent character and can reduce operating voltage, thereby increase power efficiency as the device of substrate material, and and then improvement watt consumption.
Though described preferred implementation of the present invention for illustration purposes, it will be understood by those skilled in the art that various improvement, increase and alternative also are possible, the scope and spirit of the present invention that do not deviate from appended claims and limited.
Industrial usability
According to the present invention, organic electroluminescent compounds can have high-luminous-efficiency and can have excellent material lifetime, can be used for preparing the OLED device with extremely superior working life.
Claims (10)
1. organic electroluminescent compounds of representing by following Chemical formula 1:
Chemical formula 1
Wherein:
Ring A represents
Ring C represents
Ring B represents
X
1To X
4Represent CR independently
3Or N;
Y
1And Y
2Represent independently singly-bound ,-O-,-S-,-C (R
11) (R
12)-,-Si (R
13) (R
14)-or-N (R
15)-, gets rid of wherein Y
1And Y
2It all is single bonded situation;
R
1To R
3Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted 5-to 7-unit Heterocyclylalkyl, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl Cycloalkylfused with one or more (C3-C30), with replacement or the first Heterocyclylalkyl of unsubstituted one or more aromatic ring condensed 5-to 7-, with replacement or unsubstituted one or more aromatic ring condensed (C3-C30) cycloalkyl,-NR
16R
17,-SiR
18R
19R
20,-SR
21,-OR
22, cyano group, nitro or hydroxyl; Perhaps replacement that they can be by having or do not have condensed ring or unsubstituted (C3-C30) alkenylene or replacement or unsubstituted (C3-C30) alkylidene group link to each other with adjacent substituting group and form alicyclic ring and monocycle or many cyclophanes ring, and the carbon atom of described alicyclic ring and monocycle or many cyclophanes ring can be replaced by one or more heteroatomss that are selected from N, O and S;
R
11To R
22Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl, replacement or unsubstituted 5-to 7-unit's Heterocyclylalkyl or replacement or unsubstituted (C3-C30) cycloalkyl independently; Perhaps replacement that they can be by having or do not have condensed ring or unsubstituted (C3-C30) alkenylene or replacement or unsubstituted (C3-C30) alkylidene group link to each other with adjacent substituting group and form alicyclic ring and monocycle or many cyclophanes ring, and the carbon atom of described alicyclic ring and monocycle or many cyclophanes ring can be replaced by one or more heteroatomss that are selected from N, O and S;
L
1Expression singly-bound, replacement or unsubstituted (C6-C30) arylidene, replacement or unsubstituted (C2-C30) heteroarylidene, replacement or unsubstituted (C3-C30) ring alkylidene group ,-L
2-L
3-or-L
3-L
2-;
L
2Expression replaces or unsubstituted (C6-C30) arylidene;
L
3Expression replaces or unsubstituted (C2-C30) heteroarylidene;
Ar
1And Ar
2Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl independently;
O represents 1 to 4 integer, and when o be during more than or equal to 2 integer, each R
1Can be identical or differ from one another;
P represents 1 or 2 integer, and when p represents 2, each R
2Can be identical or differ from one another; And
Described Heterocyclylalkyl, heteroarylidene and heteroaryl comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P.
2. organic electroluminescent compounds as claimed in claim 1 is characterized in that, each substituent R
1To R
3, L
1, L
2, L
3, Ar
1, Ar
2And R
11To R
22Can also be replaced by one or more substituting groups that are selected from down group: deuterium, halogen, (C1-C30) alkyl, (C1-C30) alkyl that halogen replaces, (C6-C30) aryl, (C2-C30) heteroaryl, (C6-C30) (C2-C30) heteroaryl of alkyl replacement, (C6-C30) (C2-C30) heteroaryl of aryl replacement, (C3-C30) cycloalkyl, 5-to 7-unit Heterocyclylalkyl, three (C1-C30) alkyl silyl, three (C6-C30) aryl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, the N-carbazyl, two (C1-C30) alkylamino, two (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, two (C6-C30) aryl boryl, two (C1-C30) alkyl boryl, (C1-C30) alkyl (C6-C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carboxyl, nitro and hydroxyl.
3. organic electroluminescent compounds as claimed in claim 1 is characterized in that, and is described
Be selected from following structure:
Wherein, R
1, R
2, R
11To R
15, o and p definition identical with the definition in the described Chemical formula 1 of claim 1.
4. organic electroluminescent compounds as claimed in claim 3 is characterized in that, this compound is selected from following compound:
5. organic electroluminescence device, described device comprises as each described organic electroluminescent compounds among the claim 1-4.
6. organic electroluminescence device as claimed in claim 5 is characterized in that described device comprises first electrode; Second electrode; And inserting one or more layers organic layer between described first electrode and second electrode, wherein said organic layer comprises one or more organic electroluminescent compounds and one or more phosphorescent dopants.
7. organic electroluminescence device as claimed in claim 6 is characterized in that, described organic layer also comprises one or more amine compound that is selected from aromatic amine compound and styryl aromatic amine compound.
8. organic electroluminescence device as claimed in claim 6, it is characterized in that described organic layer also comprises one or more metals that is selected from down group: the organo-metallic of the 1st family, the 2nd family, period 4 and period 5 transition metal, lanthanide series metal and d-transition element in the periodic table of elements.
9. organic electroluminescence device as claimed in claim 7 is characterized in that described organic layer comprises electroluminescence layer and charge generation layer.
10. organic electroluminescence device as claimed in claim 7 is characterized in that described organic layer also comprises the organic electro luminescent layer of one or more layers red-emitting, green glow and blue light, with the emission white light.
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| KR10-2011-0092141 | 2011-09-09 | ||
| KR1020110092141A KR20120030941A (en) | 2010-09-20 | 2011-09-09 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| PCT/KR2011/006855 WO2012039561A1 (en) | 2010-09-20 | 2011-09-16 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2013544759A (en) | 2013-12-19 |
| TW201224111A (en) | 2012-06-16 |
| KR20120030941A (en) | 2012-03-29 |
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