WO2020237835A1 - 一种螺二芴类有机电致发光化合物及有机电致发光器件 - Google Patents
一种螺二芴类有机电致发光化合物及有机电致发光器件 Download PDFInfo
- Publication number
- WO2020237835A1 WO2020237835A1 PCT/CN2019/100149 CN2019100149W WO2020237835A1 WO 2020237835 A1 WO2020237835 A1 WO 2020237835A1 CN 2019100149 W CN2019100149 W CN 2019100149W WO 2020237835 A1 WO2020237835 A1 WO 2020237835A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substituted
- unsubstituted
- group
- compound
- derivative
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 78
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000005525 hole transport Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 32
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 32
- 239000000706 filtrate Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000004440 column chromatography Methods 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- -1 oxyfluorenyl Chemical group 0.000 claims description 11
- 238000005401 electroluminescence Methods 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 125000004306 triazinyl group Chemical group 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000005561 phenanthryl group Chemical group 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical group C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 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 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- BKQXUNGELBDWLS-UHFFFAOYSA-N 9,9-diphenylfluorene Chemical group C1=CC=CC=C1C1(C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BKQXUNGELBDWLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 39
- 230000000052 comparative effect Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000010410 layer Substances 0.000 description 31
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 229940125797 compound 12 Drugs 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 238000001308 synthesis method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 229940125898 compound 5 Drugs 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000008204 material by function Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 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 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- 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 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- SPDPTFAJSFKAMT-UHFFFAOYSA-N 1-n-[4-[4-(n-[4-(3-methyl-n-(3-methylphenyl)anilino)phenyl]anilino)phenyl]phenyl]-4-n,4-n-bis(3-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 SPDPTFAJSFKAMT-UHFFFAOYSA-N 0.000 description 1
- HVZMNJSQXYOADV-UHFFFAOYSA-N 2'-tert-butyl-1,1'-spirobi[fluorene] Chemical group C(C)(C)(C)C=1C2(C3=CC4=CC=CC=C4C3=CC1)C=CC=C1C3=CC=CC=C3C=C12 HVZMNJSQXYOADV-UHFFFAOYSA-N 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical group C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- CXOITOXMGBMFSS-UHFFFAOYSA-N CC(C)(C)c(cc1)cc2c1-c1ccccc1C21c2cc([Br]=C)ccc2-c2ccccc12 Chemical compound CC(C)(C)c(cc1)cc2c1-c1ccccc1C21c2cc([Br]=C)ccc2-c2ccccc12 CXOITOXMGBMFSS-UHFFFAOYSA-N 0.000 description 1
- HAFODDVYCFRCCZ-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1-c1ccc(C(C)(C)C)cc1C1(c(cc(cc2)Br)c2-c2ccccc12)O Chemical compound CC(C)(C)c(cc1)ccc1-c1ccc(C(C)(C)C)cc1C1(c(cc(cc2)Br)c2-c2ccccc12)O HAFODDVYCFRCCZ-UHFFFAOYSA-N 0.000 description 1
- CPGSOVMQTDBNSB-UHFFFAOYSA-N CC(C)(C)c(cc1C23c(cc(cc4)N(c(cc5)cc6c5-c5ccccc5C6(C)C)c5cccc(-c6nc(-c7ccccc7)nc(-c7ccccc7)n6)c5)c4-c4ccc(C(C)(C)C)cc24)ccc1-c1c3cc(C(C)(C)C)cc1 Chemical compound CC(C)(C)c(cc1C23c(cc(cc4)N(c(cc5)cc6c5-c5ccccc5C6(C)C)c5cccc(-c6nc(-c7ccccc7)nc(-c7ccccc7)n6)c5)c4-c4ccc(C(C)(C)C)cc24)ccc1-c1c3cc(C(C)(C)C)cc1 CPGSOVMQTDBNSB-UHFFFAOYSA-N 0.000 description 1
- BBKNCZFSPQICQT-UHFFFAOYSA-N CC(C)(C)c(cc1C23c4cc(Br)ccc4-c4ccccc24)ccc1-c1c3cc(C(C)(C)C)cc1 Chemical compound CC(C)(C)c(cc1C23c4cc(Br)ccc4-c4ccccc24)ccc1-c1c3cc(C(C)(C)C)cc1 BBKNCZFSPQICQT-UHFFFAOYSA-N 0.000 description 1
- QVCVCWMQLQCHRG-ZHSUKTGHSA-N CC/C=C(\CC(C)N(c(cc1)ccc1-c1ccccc1)c(cc1)cc(C2(C)C)c1-c1c2cccc1)/c1ccccc1 Chemical compound CC/C=C(\CC(C)N(c(cc1)ccc1-c1ccccc1)c(cc1)cc(C2(C)C)c1-c1c2cccc1)/c1ccccc1 QVCVCWMQLQCHRG-ZHSUKTGHSA-N 0.000 description 1
- QRMLAMCEPKEKHS-UHFFFAOYSA-N CC1(C)c(cc(cc2)Nc(cc3)ccc3-c3ccccc3)c2-c2ccccc12 Chemical compound CC1(C)c(cc(cc2)Nc(cc3)ccc3-c3ccccc3)c2-c2ccccc12 QRMLAMCEPKEKHS-UHFFFAOYSA-N 0.000 description 1
- RKNRWKSOJAUSDU-UHFFFAOYSA-N Cc1ccccc1C(C=C)=C Chemical compound Cc1ccccc1C(C=C)=C RKNRWKSOJAUSDU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- DKJYIUXQOKGASX-UHFFFAOYSA-N c(cc1)ccc1-c(ccc(Nc1ccccc1)c1)c1-c1ccccc1 Chemical compound c(cc1)ccc1-c(ccc(Nc1ccccc1)c1)c1-c1ccccc1 DKJYIUXQOKGASX-UHFFFAOYSA-N 0.000 description 1
- 150000001716 carbazoles Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
Definitions
- the invention belongs to the technical field of organic electroluminescence materials, and specifically relates to a spirobifluorene organic electroluminescence compound and an organic electroluminescence device.
- OLED Organic light-emitting devices
- fluorescent materials emit light through recombination of holes injected from the positive electrode and electrons injected from the negative electrode.
- This self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, fast response, and good temperature adaptability. It is also ultra-thin and can be fabricated on flexible panels. It is widely used in mobile phones, tablet computers, TVs, and lighting. And other fields.
- the organic electroluminescent device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers. Various functional materials are superimposed on each other according to the purpose to form an organic electroluminescent device.
- As a current device when a voltage is applied to the electrodes at both ends of the organic electroluminescence device, positive and negative charges are generated in the organic layer functional material film through the action of an electric field, and the positive and negative charges are further recombined in the light-emitting layer to generate light. For electroluminescence.
- the material designed by the present invention introduces tert-butyl on the spirobifluorene, which increases the torque and freedom of the material molecules, reduces the flatness of the material, and thereby reduces the crystallinity of the material .
- the reduced planarity of material molecules can effectively improve the use effect and scope of the material.
- the increase of the material's molecular torque and degree of freedom effectively improves the hole transport capability of this type of material, adjusts the HOMO energy level of the hole transport material, and greatly reduces the driving voltage of the organic electroluminescent device, effectively reducing energy consumption , And greatly improve the life of organic electroluminescent devices.
- the present invention provides a spirobifluorene organic electroluminescent compound and an organic electroluminescent device.
- a spirobifluorene organic electroluminescent compound its structural formula is as follows:
- Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted C6-C24 aromatic hydrocarbon groups, substituted or unsubstituted C5-C24 heteroaromatic hydrocarbon groups;
- R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C6-C18 aromatic hydrocarbon groups, substituted or unsubstituted C5-C18 heteroaromatic hydrocarbon group, and R 1 , R 2 , and R 3 are not hydrogen at the same time.
- Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted phenyl and its derivative groups, substituted or unsubstituted naphthyl and its derivative groups, substituted or unsubstituted anthryl and its Derivative group, substituted or unsubstituted phenanthrene group and its derivative group, substituted or unsubstituted fluorenyl group and its derivative group, substituted or unsubstituted carbazole group and its derivative group, substituted or Unsubstituted furanyl and its derivative groups, substituted or unsubstituted thienyl and its derivative groups, substituted or unsubstituted pyrimidinyl and its derivative groups, substituted or unsubstituted pyridyl and its derivatives Groups, substituted or unsubstituted triazinyl and its derivative groups;
- R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted phenyl and its derivative groups, substituted or unsubstituted The naphthyl group and its derivative group, substituted or unsubstituted anthracenyl group and its derivative group, substituted or unsubstituted phenanthryl group and its derivative group, substituted or unsubstituted fluorenyl group and its derivative group Groups, substituted or unsubstituted carbazolyl and its derivative groups, substituted or unsubstituted furyl and its derivative groups, substituted or unsubstituted thienyl and its derivative groups, substituted or unsubstituted Pyrimidine group and its derivative group, substituted or unsubstituted pyridyl group and its derivative group, substituted or unsubstituted triazinyl group and its derivative group
- Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted phenyl, benzyl, phenethyl, naphthyl, anthryl, phenanthryl, fluorenyl, oxyfluorenyl, 9,9- Spirobifluorene group, 9,9-dimethylfluorene group, 9,9-diphenylfluorene group, carbazolyl, N-ethylcarbazolyl, 4-hydroxycarbazolyl, benzocarbaze Azolyl, furyl, thienyl, phenylpyrimidinyl, pyrimidinyl, pyridyl, triazinyl;
- R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Phenyl, biphenyl, 9,9-dimethylfluorene groups, and R 1 , R 2 , and R 3 are not hydrogen at the same time.
- the substituted substituent is selected from at least one of the following atoms or groups: deuterium, hydroxyl, cyano, mono-deuterium methyl, di-deuterium methyl, tri-deuterium methyl, C1-C4 straight Chain or branched alkyl, C6-C18 aromatic hydrocarbon group, C5-C24 heteroaromatic hydrocarbon group.
- Ar1 and Ar2 are each independently selected from the following groups:
- R1, R2, and R3 are each independently selected from the following atoms or groups:
- R1, R2, and R3 are not H at the same time.
- the spirobifluorene organic electroluminescent compound is one of the following structural formula compounds:
- the present invention also provides a preparation method of spirobifluorene organic electroluminescent compound, which comprises the following steps:
- the general formula is Add the compound I to anhydrous THF, lower the temperature to -78°C, add n-butyl lithium dropwise, the molar ratio of compound I to n-butyl lithium is 1:1.1, after 30-50 minutes of reaction, the general structure will be Add the anhydrous THF solution of compound II of, and continue the reaction at -78°C for 2-4h. After quenching, slowly return to room temperature and add dichloromethane and water to extract and separate. The dichloromethane phase is washed with water, dried, and concentrated under reduced pressure. After analysis and purification, the general structure is obtained as Compound III;
- the general structure of compound IV is Compound V, sodium tert-butoxide, Pd 2 (dba) 3 : tri-tert-butyl phosphine molar ratio 1:1.1:1.1:0.05-0.06: 0.01-0.06 was added to toluene, after the addition, the temperature was raised to reflux reaction 5 After the reaction is completed, it is cooled to room temperature and then added with water and stirred for 15-30 minutes and then filtered. The organic phase is obtained after the filtrate is separated. The organic phase is dried and concentrated by column chromatography to purify the spirobifluorene organic electroluminescent compound.
- An organic electroluminescence device comprising an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode, a hole transport layer and/or
- the electron blocking layer includes at least one of the above-mentioned spirobifluorene organic electroluminescent compounds.
- An organic electroluminescent device comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode.
- the hole transport layer includes at least one of the above-mentioned spirobifluorenes. Electroluminescent compounds.
- the organic electroluminescent compound material designed in the present invention introduces a tert-butyl spirobifluorene structure, which has good aromaticity and thermal stability; at the same time, tert-butyl is a good electron-donating group, which can greatly increase the spirobifluorene structure.
- the electron cloud density of difluorene gives this type of material unique optoelectronic properties, and this structure reduces the HOMO energy level of the material itself due to its higher electron cloud density, thereby reducing the hole injection layer (HIL) and holes
- HIL hole injection layer
- HTL potential energy barrier between the transport layers (HTL) is more conducive to the transport of holes, thereby effectively reducing the driving voltage and energy consumption of the organic electroluminescent device.
- tert-butyl greatly reduces the flatness and crystallinity of the material, thereby greatly expanding the application range of this type of material, which can significantly improve the production yield of organic electroluminescent devices and reduce the manufacturing cost of organic electroluminescent devices .
- Connecting the symmetrical or asymmetrical branched chain structure greatly improves the torque and richness of the material molecules, controls the freedom of the material molecules, directly and effectively destroys the planarity and crystallinity of the molecules, avoids the aggregation of materials, and can have Effectively increase the glass transition temperature of the material.
- the hole transport rate of this type of material can be effectively adjusted and controlled to further improve the hole transport performance of the material, thereby increasing the service life and luminous efficiency of the device.
- compounds G69 and G74 are supported by Chain I and branch chain II have strong torque and steric hindrance, which effectively inhibits the free rotation and twisting of the material.
- the two materials have very low driving voltage, good lifetime and luminous efficiency.
- deuterium (D) is an isotope of hydrogen (H).
- the introduction of deuterium (D) can correspondingly increase the thermal stability of the material, increase the service life of the material, and thereby increase the service life of the organic electroluminescent device.
- compound G86 whose branched chain III is compared to the above-mentioned branched chain II, has a certain increase in device life due to the introduction of deuterium.
- the material designed by the present invention has a greatly improved life, a greatly improved efficiency, and a greatly reduced driving voltage.
- the filtrate is obtained by filtration.
- the organic phase is obtained after the filtrate is separated.
- the organic phase uses anhydrous sulfuric acid
- the magnesium was dried, spin-dried and purified by column chromatography to obtain high-purity G20 (8.43 g, yield 62.4%), MS (EI): 843 (M + ).
- Steps (1) and (2) are basically the same as those in Example 2.
- Step (3) is as follows:
- compound 9 (10g, 22.2mmol), compound 10 (1.1eq, 321g/mol, 24.4mmol, 7.84g), sodium tert-butoxide (1.1eq, 96.1g/mol, 24.4mmol, 2.35g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 1.11mmol, 1.02g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 1.11mmol, 0.223g), toluene (100g, 10 times the mass of compound 9) was added to the reaction flask, after the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 2.
- Step (3) is as follows:
- Steps (1) and (2) are basically the same as those in Example 2.
- Step (3) is as follows:
- compound 9 (10g, 22.2mmol), compound 15 (1.1eq, 378g/mol, 24.4mmol, 9.22g), sodium tert-butoxide (1.1eq, 96.1g/mol, 24.4mmol, 2.35g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 1.11mmol, 1.02g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 1.11mmol, 0.223g), toluene (100g, 10 times the mass of compound 9) was added to the reaction flask, after the addition, the temperature was raised to reflux and reacted for 5h.
- Step (1), step (2), and step (3) are basically the same as those in Example 1.
- Step (4) is as follows:
- compound 5 (10g, 17.8mmol), compound 16 (1.1eq, 516g/mol, 19.6mmol, 10.1g), sodium tert-butoxide (1.1eq, 96.1g/mol, 19.6mmol, 1.88g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.89mmol, 0.81g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.89mmol, 0.18g), toluene (100g, 10 times the mass of compound 5) was added to the reaction flask, after the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- compound 12 (10g, 19.8mmol), compound 17 (1.1eq, 486.21g/mol, 21.7mmol, 10.54g), sodium tert-butoxide (1.1eq, 96.1g/mol, 21.7mmol) , 2.09g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.99mmol, 0.91g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.99mmol, 0.2g), Toluene (100g, 10 times the mass of compound 12) was added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- compound 12 (10g, 19.8mmol), compound 18 (1.1eq, 514.24g/mol, 21.7mmol, 11.16g), sodium tert-butoxide (1.1eq, 96.1g/mol, 21.7mmol) , 2.09g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.99mmol, 0.91g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.99mmol, 0.2g), Toluene (100g, 10 times the mass of compound 12) was added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- compound 12 (10g, 19.8mmol), compound 20 (1.1eq, 378.2g/mol, 21.7mmol, 8.21g), sodium tert-butoxide (1.1eq, 96.1g/mol, 21.7mmol) , 2.09g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.99mmol, 0.91g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.99mmol, 0.2g), Toluene (100g, 10 times the mass of compound 12) was added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- compound 12 (10g, 19.8mmol), compound 21 (1.1eq, 321.15g/mol, 21.7mmol, 6.97g), sodium tert-butoxide (1.1eq, 96.1g/mol, 21.7mmol) , 2.09g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.99mmol, 0.91g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.99mmol, 0.2g), Toluene (100g, 10 times the mass of compound 12) was added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5h.
- Steps (1) and (2) are basically the same as those in Example 4.
- Step (3) is as follows:
- compound 12 (10g, 19.8mmol), compound 22 (1.1eq, 321.15g/mol, 21.7mmol, 6.97g), sodium tert-butoxide (1.1eq, 96.1g/mol, 21.7mmol) , 2.09g), Pd 2 (dba) 3 (5%eq, 915.72g/mol, 0.99mmol, 0.91g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.99mmol, 0.2g), Toluene (100g, 10 times the mass of compound 12) was added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5h.
- Steps 1-3 are basically the same as those in Example 1.
- compound 5 (9g, 562.2g/mol 16mmol), compound 23 (1.1eq, 426.17g/mol, 17.6mmol, 7.5g), sodium tert-butoxide (1.1eq, 96.1g/mol, 17.6mmol) , 1.69g), Pd 2 (dba) 3 (5%eq, 0.8mmol, 0.732g), tri-tert-butylphosphine (5%eq, 202.317g/mol, 0.8mmol, 1.62g), toluene (90g, compound 10 times the mass of 5) was added to the reaction flask, after the addition was completed, the temperature was raised to reflux for 5h.
- HAT-CN hole injection layer
- HTL hole transport layer
- 9,10-Bis(2-naphthyl)anthraces (ADN) of blue EML is formed by vacuum evaporation as the light-emitting layer to form 2,5,8,11-Tetra-Butyl- Perilene (t-Bu-Perylene) is a dopant material, doped with about 5% of 25 nm thickness to form a light-emitting layer, and a mixture of ETM and LiQ with a thickness of 35 nm is deposited on the top at a ratio of 1:1 to the electron transport layer (ETL ), and then vapor-deposit LiQ with a thickness of 2 nanometers on the electron injection layer (EIL).
- ETL electron transport layer
- magnesium (Mg) and silver (Ag) were mixed in a ratio of 9:1 on the cathode and vapor-deposited with a thickness of 15 nanometers, and a thickness of 65 nanometers of N4, N4′-BIS was deposited on the cathode sealing layer.
- the surface of the cathode is sealed with a UV curing adhesive and a seal cap containing a desiccant to protect the organic electroluminescent device from oxygen or moisture in the atmosphere while manufacturing the organic electroluminescent device.
- HTL hole transport layer
- the organic electroluminescent device prepared by using the compound of the present invention has a greatly reduced voltage and a significantly improved luminous efficiency compared with the control example. It can be seen that the compound of the present invention can greatly reduce the driving voltage of the device, greatly reduce the power consumption, and significantly improve the luminous efficiency. In addition, by reducing the driving voltage, the life span of the organic electroluminescent device is significantly improved.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
公开了一种螺二芴类有机电致发光化合物及有机电致发光器件，该螺二芴类有机电致发光化合物结构式如式I所示。该类化合物能够作为有机电致发光材料应用，与对比技术相比，该材料分子的平面性降低能够有效提高材料的使用效果及使用范围，材料分子扭矩及自由度的增大有效改善了该类材料的空穴传输能力，调节了空穴传输材料的HOMO能级，进而大大降低了有机电致发光器件的驱动电压，有效较少能耗，并大幅度提高了有机电致发光器件的寿命。
Description
本发明属于有机电致发光材料技术领域，具体涉及一种螺二芴类有机电致发光化合物及有机电致发光器件。
有机电致发光器件(Organic Light-emitting Devices,OLED)是利用如下原理的自发性发光器件：当施加电场时，荧光物质通过正极注入的空穴和负极注入的电子的重新结合而发光。这种自发光器件，具有电压低、亮度高、视角宽、响应快、温度适应性好等特性，并且超薄，能制作在柔性面板上等优点，广泛应用于手机、平板电脑、电视、照明等领域。
有机电致发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成有机电致发光器件。作为电流器件，当对有机电致发光器件的两端电极施加电压，并通过电场作用在有机层功能材料膜层中产生正负电荷，正负电荷进一步在发光层中复合，产生光，此过程为电致发光。
对于有机电致发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现有机电致发光器件性能的不断提升，不但需要有机电致发光器件的结构和制作工艺的创新，更需要有机电致光电功能材料的不断研究和创新，创制出更高性能的有机电致功能材料。
就当前有机电致发光产业的实际需求而言，目前有机电致发光材料的发展还远远不够，落后于面板制造企业的要求。
就目前现有技术US2017331039A1对比而言，本发明设计的材料由于在螺二芴上引入叔丁基，增大了材料分子的扭矩及自由度，降低了材料的平面性，进而降低材料的结晶性。材料分子的平面性降低能够有效提高材料的使用效果及使用范围。材料分子扭矩及自由度的增大有效改善了该类材料的空穴传输能力，调节了空穴传输材料的HOMO能级，进而大大降低了有机电致发光器件的驱动电压，有效较少能耗,并大幅度提高了有机电致发光器件的寿命。
发明内容
发明目的：针对上述技术问题，本发明提供了一种螺二芴类有机电致发光化合物及有机电致发光器件。
为了达到上述发明目的，本发明所采用的技术方案如下：
一种螺二芴类有机电致发光化合物，其结构式如下所示：
其中，Ar
1、Ar
2各自独立的选自取代或未取代的C6-C24芳香族烃基、取代或未取代的C5-C24杂芳香族烃基；
R
1、R
2、R
3各自独立的选自氢、取代或未取代的C1-C4的直链或支链烷基、取代或未取代的C6-C18的芳香族烃基，取代或未取代的C5-C18杂芳香族烃基，且R
1、R
2、R
3不同时为氢。
优选的，Ar
1、Ar
2各自独立的选自取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团；
R
1、R
2、R
3各自独立的选自氢，取代或未取代的C1-C4的直链或支链烷基，取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团。
进一步优选的，Ar
1、Ar
2各自独立的选自取代或未取代的苯基、苯甲基、苯乙基、萘基、蒽基、菲基、芴基、氧芴基、9,9-螺二芴基团、9,9-二甲基芴基团、9,9-二苯基芴基团、咔唑基、N-乙基咔唑基、4-羟基咔唑基、苯并咔唑基、呋喃基、噻吩基、苯基嘧啶基、嘧啶基、吡啶基、三嗪基；
R
1、R
2、R
3各自独立的选自氢，取代或未取代的甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基、联苯基、9,9-二甲基芴基团，且R
1、R
2、R
3不同时为氢。
进一步优选的，所述取代的取代基选自以下原子或基团中的至少一种：氘、羟基、氰 基、单氘甲基、双氘甲基、三氘甲基、C1-C4的直链或支链烷基、C6-C18芳香族烃基、C5-C24杂芳香族烃基。
进一步优选的，Ar1、Ar2各自独自选自以下基团：
所述R1、R2、R3各自独自选自以下原子或基团：
且R1、R2、R3不同时为H。
进一步优选的，所述螺二芴有机电致发光化合物为下列结构式化合物中的一种：
本发明还提供了一种螺二芴类有机电致发光化合物的制备方法，包括以下步骤：
(1)惰性气体保护下将结构通式为
的化合物Ⅰ加入到无水THF中，降温至-78℃，滴加正丁基锂，化合物Ⅰ与正丁基锂的摩尔比为1:1.1，反应30-50min后，将将结构通式为
的化合物Ⅱ的无水THF溶液加入，-78℃下继续反应2-4h，淬灭后缓慢恢复室温加入二氯甲烷和水萃取分液，二氯甲烷相水洗，干燥，减 压浓缩后柱层析提纯后得到结构通式为
的化合物Ⅲ；
(2)化合物Ⅲ在异丙醇和盐酸共沸的条件下反应后抽滤得到结构通式为
的化合物Ⅳ；
(3)惰性气体保护下，将化合物Ⅳ、结构通式为
的化合物Ⅴ、叔丁醇钠、Pd
2(dba)
3：三叔丁基膦按摩尔比1:1.1:1.1:0.05-0.06：0.01-0.06加入到甲苯中，加料完毕后升温至回流反应5-8h，反应完毕后降至室温后加水搅拌15-30min后过滤，滤液分液后得有机相，有机相干燥后浓缩柱层析提纯即可得到所述螺二芴类有机电致发光化合物。
上述的螺二芴类有机电致发光化合物在制备发光器件中的应用。
一种有机电致发光器件，包括阳极、空穴注入层、空穴传输层、电子阻隔层、发光层、空穴阻隔层、电子传输层、电子注入层和阴极，空穴传输层和/或电子阻隔层中包括至少一种上述的螺二芴类有机电致发光化合物。
一种有机电致发光器件，包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，空穴传输层中包括至少一种上述的螺二芴类有机电致发光化合物。
本发明的有益效果：
本发明设计的有机电致发光化合物材料引入叔丁基的螺二芴结构，该结构具有良好的芳香性及热稳定性；同时叔丁基是很好的供电子基团，能够大幅度增加螺二芴的电子云密度，使该类材料具有独特的光电学性质，并且该结构由于其较高的电子云密度使得材料本身的HOMO能级降低，进而降低空穴注入层(HIL)与空穴传输层(HTL)之间势能垒，更有利于空穴的传输，进而有效降低了有机电致发光器件的驱动电压及能耗。叔丁基的引入大大降低了材料的平面性及结晶性，进而大幅度扩展了该类材料的使用范围，能够明显提高有机电致发光器件的制备良率，降低有机电致发光器件的制造成本。
连接对称或非对称的支链结构，大幅度提高了材料分子的扭矩及丰富度控制了材料分子 的自由度，直接有效的破坏了分子的平面性及结晶性，避免材料的聚集作用，能有有效提高材料的玻璃化温度。通过调整该材料分子的支链结构能够有效调节并控制该类材料的空穴传输速率，以进一步提高材料的空穴传输性能，进而提高器件的使用寿命及发光效率，例如化合物G69、G74由于支链I及支链II具有很强的扭矩及空间位阻，有效抑制了材料的自由旋转及扭动。
因此经过器件验证，该两款材料均具有很低的驱动电压、良好的寿命及发光效率。
另外，氘(D)即氢(H)的同位素，氘(D)的引入能够相应的增加材料的热稳定性，提高材料的使用寿命，进而提高有机电致发光器件的使用寿命。例如化合物G86,其支链III，相比较上述支链II，由于氘的引入，其器件的寿命有一定的提高。
综上：本发明设计的材料相较对比文件，寿命有极大的提高，效率大幅度提高，驱动电压也有非常大的降低。
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1：
化合物G20的具体合成方法如下：
(1)将化合物1(0.1mol，25.7g)、FeCl3(0.1eq，0.01mol，1.62g)、CS
2(514g，化合物1的20倍质量)加入到反应瓶中，冰浴下加入氯代叔丁烷(1.1eq，0.11mol，10.18g)，加完后缓慢恢复室温反应10h后,反应液倒入冰块(1028g，冰块质量为CS
2的2倍质量)中，滴加盐酸至体系pH至2-3，再加入二氯甲烷(1028g，CS
2的2倍质量)进行萃取，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物2的粗品，经过柱层析提纯后得到化合物2纯品(18.3g，收率58.3％)，MS(EI)：314(M
+)；
(2)氮气保护下将化合物3(1eq，57mmol，16.5g)、无水THF(165g，化合物3的10倍质量)加入到反应瓶中，液氮降温至-78℃，滴加正丁基锂(1.1eq，62.7mmol)，反应30min后，将化合物2(18g，57mmol)、无水THF(180g，化合物2的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入饱和氯化铵溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物4的粗品，经过柱层析提纯后得到化合物4纯品(10.5g，收率31.8％)，MS(EI)：580(M
+)；
(3)将化合物4(10g，17mmol)加入到异丙醇(100g，化合物4的10倍质量)中，再滴加盐酸(1M，100g，化合物4的10倍质量)，加热共沸反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物5(9.4g，收率97％)，MS(EI)：562(M
+)；
(4)氮气保护下，将化合物5(9g，16mmol)、化合物6(1.1eq,361g/mol,17.6mmol，6.35g)、叔丁醇钠(1.1eq，96.1g/mol,17.6mmol，1.69g)、Pd
2(dba)
3(5％eq，0.8mmol，0.732g)、三叔丁基膦(5％eq，202.317g/mol，0.8mmol，1.62g)、甲苯(90g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G20(8.43g，收率62.4％)，MS(EI)：843(M
+)。
实施例2：
化合物G116的具体合成方法如下：
(1)氮气保护下化合物7(1eq，288g/mol,57mmol，16.4g)、无水THF(164g，化合物7的10倍质量)加入到反应瓶中.液氮降温至-78℃，滴加正丁基锂(1.1eq,62.7mmol)，反应30min后，将化合物1(14.7g，257.97g/mol,57mmol)、无水THF(147g，化合物2的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入氯化铵 溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物8的粗品，经过柱层析提纯后得到化合物8纯品(15.2g，收率57.1％)，MS(EI)：468(M
+)；
(2)将化合物8(15g，32mmol)加入到异丙醇(150g，化合物8的10倍质量)中，再滴加盐酸(1M，150g，化合物8的10倍质量)，加热至共沸，反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物9(13.8g，收率95.8％)，MS(EI)：450(M
+)；
(3)氮气保护下，将化合物9(13.5g，30mmol)、化合物6(1.1eq,361g/mol,33mmol，11.91g)、叔丁醇钠(1.1eq，96.1g/mol,33mmol，3.17g)、Pd
2(dba)
3(5％eq，915.72g/mol，1.65mmol，1.51g)、三叔丁基膦(5％eq，202.317g/mol，1.65mmol，3.34g)、甲苯(135g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G116(12.6g，收率57.5％)，MS(EI)：731(M
+)。
实施例3：
化合物G148的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物10(1.1eq,321g/mol,24.4mmol，7.84g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd
2(dba)
3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G148(7.63g，收率49.9％)，MS(EI)：691(M
+)。
实施例4：
化合物G154的具体合成方法如下：
(1)氮气保护下将化合物3(1eq，344.11g/mol，29mmol，10g)、无水THF(100g，化合物3的10倍质量)加入到反应瓶中，液氮降温至-78℃，滴加正丁基锂(1.1eq，31.9mmol)，反应30min后，将化合物1(9.48g，257.97g/mol，29mmol)、无水THF(94.8g，化合物1的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入氯化铵溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物11的粗品，经过柱层析提纯后得到化合物11纯品(8.32g，收率54.7％)，MS(EI)：524(M
+)；
(2)将化合物11(8g，15.2mmol)加入到异丙醇(80g，化合物11的10倍质量)中，再滴加盐酸(1M，80g，化合物11的10倍质量)，加热共沸反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物12(7.33g，收率95.3％)，MS(EI)：506(M
+)；
(3)氮气保护下，将化合物12(7g，13.8mmol)、化合物13(1.1eq,378.22g/mol,15.2mmol，5.74g)、叔丁醇钠(1.1eq，96.1g/mol,15.2mmol，1.46g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.69mmol，0.63g)、三叔丁基膦(5％eq，202.317g/mol，0.69mmol，0.139g)、甲苯(70g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯 度的G154(4.1g，收率36.9％)，MS(EI)：804(M
+)。
实施例5：
化合物G108的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物14(1.1eq,321g/mol,24.4mmol，7.84g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd
2(dba)
3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G108(8.1g，收率52.9％)，MS(EI)：691(M
+)。
实施例6：
化合物G144的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物15(1.1eq,378g/mol,24.4mmol，9.22g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd
2(dba)
3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G144(6.3g，收率37.9％)，MS(EI)：748(M
+)。
实施例7：
化合物G272的具体合成方法如下：
步骤(1)、步骤(2)、步骤(3)与实施例1中操作基本相同，步骤(4)如下：
(4)氮气保护下，将化合物5(10g，17.8mmol)、化合物16(1.1eq,516g/mol,19.6mmol，10.1g)、叔丁醇钠(1.1eq，96.1g/mol,19.6mmol，1.88g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.89mmol，0.81g)、三叔丁基膦(5％eq，202.317g/mol，0.89mmol，0.18g)、甲苯(100g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G272(7.1g，收率39.9％)，MS(EI)：998(M
+)。
实施例8：
化合物G247的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物17 (1.1eq,486.21g/mol,21.7mmol，10.54g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G247(9.6g，收率53.3％)，MS(EI)：912(M
+)。
实施例9：
化合物G251的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物18(1.1eq,514.24g/mol,21.7mmol，11.16g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G251(9.45g，收率50.8％)，MS(EI)：940(M
+)。
实施例10：
化合物G155的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物19(1.1eq,375.2g/mol,21.7mmol，8.14g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G251(7.7g，收率50.8％)，MS(EI)：801(M
+)。
实施例11：
化合物G86的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物20(1.1eq,378.2g/mol,21.7mmol，8.21g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G86(13.04g，收率51.9％)，MS(EI)：804(M
+)。
实施例12：
化合物G69的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物21 (1.1eq,321.15g/mol,21.7mmol，6.97g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G69(7.51g，收率50.8％)，MS(EI)：747(M
+)。
实施例13：
化合物G305的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物22(1.1eq,321.15g/mol,21.7mmol，6.97g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd
2(dba)
3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G305(7.46g，收率44.2％)，MS(EI)：852(M
+)。
实施例14：
化合物G307的具体合成方法如下：
步骤1-3与实施例1中操作基本相同
氮气保护下，将化合物5(9g，562.2g/mol 16mmol)、化合物23(1.1eq,426.17g/mol,17.6mmol，7.5g)、叔丁醇钠(1.1eq，96.1g/mol,17.6mmol，1.69g)、Pd
2(dba)
3(5％eq，0.8mmol，0.732g)、三叔丁基膦(5％eq，202.317g/mol，0.8mmol，1.62g)、甲苯(90g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G307(8.82g，收率60.7)，MS(EI)：908(M
+)。
以下将通过实施例和对照例对本发明进行详细的说明。下属实施例于对照例只是为了举例说明本发明，本发明的范围并不限于下述实施例和对照例。
《有机电致发光器件的制造》
应用例1:
其采用ITO作为反射层阳极基板材料，并以N
2等离子对其进行表面处理。在阳极基板上方，向空穴注入层(HIL)沉积HAT-CN 10纳米厚度的HAT-CN，在其上方选择本发明化合物G1以120纳米厚度形成空穴传输层(HTL)。在上述空穴传输层(HTL)上,真空蒸镀形成blue EML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光层，形成以2,5,8,11-Tetra-Butyl-Perilene(t-Bu-Perylene)为dopant材料，掺杂约5％的25纳米厚度形成发光层，并在上方以1:1的比例混合蒸镀35纳米厚度的ETM和LiQ到电子输送层(ETL)，之后在电子注入层(EIL)上以2纳米厚度的LiQ进行蒸镀。此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。
此外，在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封，以保护有机电致发光器件不被大气中的氧气或水分所影响的同时制造有机电致发光器件。
应用例2-11
分别以化合物G20、G69、G74、G86、G148、G154、G155、G247、G251、G272作为空穴传输层(HTL)物质，其他部分与应用例1一致，据此制作出应用例2～11的有机电致发光器件。
对照例1、2
与应用例1的区别在于，使用对比文件US2017331039A1中的化合物1-13及1-21代替本发明的化合物作为空穴传输层，其余与应用例1相同。
上述应用例制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm
2的条件下测定的，结果如表1所示。
表1：
由如上表1的实验对比数据可知，采用本发明所述的化合物制备的有机电致发光器件与对照例相比，电压大幅度降低，发光效率显著提高。由此可见，本发明的化合物能使器件的驱动电压大大降低，大幅度减少了电能的消耗、显著提高了发光效率。另外通过降低驱动电压，有机电致发光器件的寿命有显著提高。
Claims (10)
- 一种螺二芴类有机电致发光化合物，其特征在于，其结构式如下所示：
其中，Ar 1、Ar 2各自独立的选自取代或未取代的C6-C24芳香族烃基、取代或未取代的C5-C24杂芳香族烃基；R 1、R 2、R 3各自独立的选自氢、取代或未取代的C1-C4的直链或支链烷基、取代或未取代的C6-C18的芳香族烃基，取代或未取代的C5-C18杂芳香族烃基，且R 1、R 2、R 3不同时为氢。 - 如权利要求1所述的螺二芴类有机电致发光化合物，其特征在于，Ar 1、Ar 2各自独立的选自取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团；R 1、R 2、R 3各自独立的选自氢，取代或未取代的C1-C4的直链或支链烷基，取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团。
- 如权利要求2所述的螺二芴类有机电致发光化合物，其特征在于，Ar 1、Ar 2各自独立的选自取代或未取代的苯基、苯甲基、苯乙基、萘基、蒽基、菲基、芴基、氧芴基、9,9-螺二芴基团、9,9-二甲基芴基团、9,9-二苯基芴基团、咔唑基、N-乙基咔唑基、4-羟基咔唑基、苯并咔唑基、呋喃基、噻吩基、苯基嘧啶基、嘧啶基、吡啶基、三嗪基；R 1、R 2、R 3各自独立的选自氢，取代或未取代的甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基、联苯基、9,9-二甲基芴基团，且R 1、R 2、R 3不同时为 氢。
- 如权利要求1～3中任一所述的螺二芴类有机电致发光化合物，其特征在于，所述取代的取代基选自以下原子或基团中的至少一种：氘、羟基、氰基、单氘甲基、双氘甲基、三氘甲基、C1-C4的直链或支链烷基、C6-C18芳香族烃基、C5-C24杂芳香族烃基。
- 如权利要求1～4中任一所述的螺二芴类有机电致发光化合物，其特征在于，Ar1、Ar2各自独自选自以下基团：
所述R1、R2、R3各自独自选自以下原子或基团：
且R1、R2、R3不同时为H。 - 如权利要求1所述的螺二芴类有机电致发光化合物，其特征在于，所述螺二芴有机电致发光化合物为下列结构式化合物中的一种：
- 一种如权利要求1-6中任一项所述的螺二芴类有机电致发光化合物的制备方法，其特征在于，包括以下步骤：(1)惰性气体保护下将结构通式为的化合物Ⅰ加入到无水THF中，降温至-78℃，滴加正丁基锂，化合物Ⅰ与正丁基锂的摩尔比为1:1.1，反应30-50min后，将将结构通式为
的化合物Ⅱ的无水THF溶液加入，-78℃下继续反应2-4h，淬灭后缓慢恢复室温加入二氯甲烷和水萃取分液，二氯甲烷相水洗，干燥，减 压浓缩后柱层析提纯后得到结构通式为
的化合物Ⅲ；
(2)化合物Ⅲ在异丙醇和盐酸共沸的条件下反应后抽滤得到结构通式为的化合物Ⅳ；
(3)惰性气体保护下，将化合物Ⅳ、结构通式为的化合物Ⅴ、叔丁醇钠、Pd 2(dba) 3：三叔丁基膦按摩尔比1:1.1:1.1:0.05-0.06：0.01-0.06加入到甲苯中，加料完毕后升温至回流反应5-8h，反应完毕后降至室温后加水搅拌15-30min后过滤，滤液分液后得有机相，有机相干燥后浓缩柱层析提纯即可得到所述螺二芴类有机电致发光化合物。
- 如权利要求1-6中任一项所述的螺二芴类有机电致发光化合物在制备发光器件中的应用。
- 一种有机电致发光器件，其特征在于，包括阳极、空穴注入层、空穴传输层、电子阻隔层、发光层、空穴阻隔层、电子传输层、电子注入层和阴极，空穴传输层和/或电子阻隔层中包括至少一种如权利要求1-6中任一项所述的螺二芴类有机电致发光化合物。
- 一种有机电致发光器件，其特征在于，包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，空穴传输层中包括至少一种如权利要求1-6中任一项所述的螺二芴类有机电致发光化合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910455726.7 | 2019-05-29 | ||
| CN201910455726.7A CN112010760B (zh) | 2019-05-29 | 2019-05-29 | 一种螺二芴类有机电致发光化合物及有机电致发光器件 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020237835A1 true WO2020237835A1 (zh) | 2020-12-03 |
Family
ID=73501010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2019/100149 WO2020237835A1 (zh) | 2019-05-29 | 2019-08-12 | 一种螺二芴类有机电致发光化合物及有机电致发光器件 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112010760B (zh) |
| WO (1) | WO2020237835A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149333A (zh) * | 2021-11-29 | 2022-03-08 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及其在有机电致发光器件中的应用 |
| CN114163339A (zh) * | 2021-11-29 | 2022-03-11 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及有机电致发光器件 |
| CN114975839A (zh) * | 2022-07-26 | 2022-08-30 | 吉林奥来德光电材料股份有限公司 | 一种有机电致发光器件、有机电致发光装置及光电设备 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548278B (zh) * | 2019-12-31 | 2021-05-28 | 南京高光半导体材料有限公司 | 一种新型有机电致发光化合物及有机电致发光器件 |
| CN112010762B (zh) * | 2020-08-18 | 2022-02-22 | 南京高光半导体材料有限公司 | 一种有机电致发光化合物及有机电致发光器件 |
| CN112349858B (zh) * | 2021-01-11 | 2021-05-18 | 南京高光半导体材料有限公司 | 一种有机电致发光器件 |
| CN113292480A (zh) * | 2021-05-25 | 2021-08-24 | 上海钥熠电子科技有限公司 | 稠环芳香胺化合物和包含其的有机电致发光显示器件 |
| CN116589365A (zh) * | 2023-04-07 | 2023-08-15 | 南京高光半导体材料有限公司 | 一种胺基化合物及有机电致发光器件 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103108859A (zh) * | 2010-09-15 | 2013-05-15 | 默克专利有限公司 | 用于有机电致发光器件的材料 |
| KR20170134163A (ko) * | 2016-05-27 | 2017-12-06 | 주식회사 엘지화학 | 유기 발광 소자 |
| CN108250083A (zh) * | 2016-12-27 | 2018-07-06 | 东进世美肯株式会社 | 新颖化合物及包含其的有机发光器件 |
| CN108658932A (zh) * | 2018-05-18 | 2018-10-16 | 长春海谱润斯科技有限公司 | 一种含有9,9’-螺二芴和二苯并噻吩的芳香胺化合物及其有机电致发光器件 |
| WO2019002190A1 (en) * | 2017-06-28 | 2019-01-03 | Merck Patent Gmbh | MATERIALS FOR ELECTRONIC DEVICES |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107121437A (zh) * | 2017-06-21 | 2017-09-01 | 陈群 | 一种折叠式双面屏幕式布匹检测装置 |
| CN110416422B (zh) * | 2018-04-28 | 2021-06-15 | 江苏三月科技股份有限公司 | 有机电致发光器件及包括其的显示器 |
| CN108795419A (zh) * | 2018-06-07 | 2018-11-13 | 长春海谱润斯科技有限公司 | 一种有机电致发光材料及其有机电致发光器件 |
-
2019
- 2019-05-29 CN CN201910455726.7A patent/CN112010760B/zh active Active
- 2019-08-12 WO PCT/CN2019/100149 patent/WO2020237835A1/zh active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103108859A (zh) * | 2010-09-15 | 2013-05-15 | 默克专利有限公司 | 用于有机电致发光器件的材料 |
| KR20170134163A (ko) * | 2016-05-27 | 2017-12-06 | 주식회사 엘지화학 | 유기 발광 소자 |
| CN108250083A (zh) * | 2016-12-27 | 2018-07-06 | 东进世美肯株式会社 | 新颖化合物及包含其的有机发光器件 |
| WO2019002190A1 (en) * | 2017-06-28 | 2019-01-03 | Merck Patent Gmbh | MATERIALS FOR ELECTRONIC DEVICES |
| CN108658932A (zh) * | 2018-05-18 | 2018-10-16 | 长春海谱润斯科技有限公司 | 一种含有9,9’-螺二芴和二苯并噻吩的芳香胺化合物及其有机电致发光器件 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149333A (zh) * | 2021-11-29 | 2022-03-08 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及其在有机电致发光器件中的应用 |
| CN114163339A (zh) * | 2021-11-29 | 2022-03-11 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及有机电致发光器件 |
| CN114149333B (zh) * | 2021-11-29 | 2024-03-29 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及其在有机电致发光器件中的应用 |
| CN114163339B (zh) * | 2021-11-29 | 2024-03-29 | 南京高光半导体材料有限公司 | 一种含有螺二芴并金刚烷主体结构的化合物及有机电致发光器件 |
| CN114975839A (zh) * | 2022-07-26 | 2022-08-30 | 吉林奥来德光电材料股份有限公司 | 一种有机电致发光器件、有机电致发光装置及光电设备 |
| CN114975839B (zh) * | 2022-07-26 | 2022-10-28 | 吉林奥来德光电材料股份有限公司 | 一种有机电致发光器件、有机电致发光装置及光电设备 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112010760B (zh) | 2021-11-02 |
| CN112010760A (zh) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020237835A1 (zh) | 一种螺二芴类有机电致发光化合物及有机电致发光器件 | |
| EP3656776B1 (en) | Indolocarbazole derivatives and organic electroluminescent devices using the same | |
| WO2017215549A1 (zh) | 一种有机电致发光化合物及其应用 | |
| WO2015067155A1 (zh) | 有机电致发光材料和有机电致发光器件 | |
| CN112250585B (zh) | 一种空穴传输材料及使用该种材料的有机电致发光器件 | |
| WO2008143416A1 (en) | Organic electroluminescent compounds and organic light emitting diode using the same | |
| CN111909212A (zh) | 一种含有6-硅基取代异喹啉配体的有机发光材料 | |
| CN113248532B (zh) | 一种有机化合物及含有该化合物的有机光电元件与应用 | |
| JP7105388B1 (ja) | 窒素含有化合物、電子部品及び電子装置 | |
| EP4119634B1 (en) | Polycyclic compound and organic electroluminescent device using the same | |
| Chen et al. | Highly efficient bipolar host material based-on indole and triazine moiety for red phosphorescent light-emitting diodes | |
| EP4238976A1 (en) | Polycyclic compound and organic light-emitting device using same | |
| KR101661925B1 (ko) | 파이렌 유도체 및 이를 이용한 유기전계발광소자 | |
| EP4006123A1 (en) | Organic electroluminescent compounds and organic electroluminescent device | |
| CN112080273B (zh) | 有机电致发光化合物及包含该化合物的有机电致发光器件 | |
| JP2018521166A (ja) | 有機エレクトロルミネッセンス材料 | |
| WO2019228430A1 (zh) | 一种含酮的化合物及其在有机电致发光器件上的应用 | |
| CN116199723B (zh) | 一种具有吡啶基氮杂二苯并呋喃配体的磷光掺杂材料及其应用 | |
| WO2018166096A1 (zh) | 一种有机发光器件及其制备方法 | |
| CN116836193A (zh) | 一种有机化合物及其应用以及包含其的有机电致发光器件 | |
| WO2020252867A1 (zh) | 一种长寿命深蓝色荧光掺杂材料及oled有机电致发光器件 | |
| CN115521212B (zh) | 有机材料、电子元件及电子装置 | |
| WO2022237816A1 (zh) | 一种含三嗪和嘧啶结构的化合物及其在有机电致发光器件上的应用 | |
| EP3998321A1 (en) | Organic light emitting compound and organic light emitting device | |
| WO2021103318A1 (zh) | P型掺杂剂及有机发光二极管 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19930692 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19930692 Country of ref document: EP Kind code of ref document: A1 |