CN114989170B - 一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物及其应用 - Google Patents
一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物及其应用 Download PDFInfo
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- CN114989170B CN114989170B CN202210797970.3A CN202210797970A CN114989170B CN 114989170 B CN114989170 B CN 114989170B CN 202210797970 A CN202210797970 A CN 202210797970A CN 114989170 B CN114989170 B CN 114989170B
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- organic electroluminescent
- phenylphenazine
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- OSZBRXNBKKWJOM-UHFFFAOYSA-N 1-phenylphenazine Chemical class C1=CC=CC=C1C1=CC=CC2=NC3=CC=CC=C3N=C12 OSZBRXNBKKWJOM-UHFFFAOYSA-N 0.000 title abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 78
- 230000003111 delayed effect Effects 0.000 claims description 3
- 125000001791 phenazinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 claims 2
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 10
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 239000000543 intermediate Substances 0.000 description 35
- 230000005525 hole transport Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 4
- UDQTXCHQKHIQMH-KYGLGHNPSA-N (3ar,5s,6s,7r,7ar)-5-(difluoromethyl)-2-(ethylamino)-5,6,7,7a-tetrahydro-3ah-pyrano[3,2-d][1,3]thiazole-6,7-diol Chemical compound S1C(NCC)=N[C@H]2[C@@H]1O[C@H](C(F)F)[C@@H](O)[C@@H]2O UDQTXCHQKHIQMH-KYGLGHNPSA-N 0.000 description 4
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- -1 amino, carbazolyl Chemical group 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940125807 compound 37 Drugs 0.000 description 4
- 229940125936 compound 42 Drugs 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 2
- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 2
- 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 2
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 229940125851 compound 27 Drugs 0.000 description 2
- 229940126540 compound 41 Drugs 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- IOMMMLWIABWRKL-WUTDNEBXSA-N nazartinib Chemical compound C1N(C(=O)/C=C/CN(C)C)CCCC[C@H]1N1C2=C(Cl)C=CC=C2N=C1NC(=O)C1=CC=NC(C)=C1 IOMMMLWIABWRKL-WUTDNEBXSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 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 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125878 compound 36 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- GFOZRCASAHKFFT-UHFFFAOYSA-N spiro[10h-acridine-9,9'-fluorene] Chemical group C12=CC=CC=C2NC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 GFOZRCASAHKFFT-UHFFFAOYSA-N 0.000 description 1
- LRDZIHIBFOPYFK-UHFFFAOYSA-N spiro[10h-acridine-9,9'-xanthene] Chemical group C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2NC2=CC=CC=C21 LRDZIHIBFOPYFK-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/18—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/18—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
- H10K85/631—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
- H10K85/636—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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
本发明属于有机电致发光材料技术领域,涉及一种以5,10‑[1,2]苯吩嗪衍生物为核心的化合物及其应用。该化合物如式(I)所示,其中X为单键或CR1R2,R1、R2独立的选自甲基;L为芳基;D为典型给电子基团。本发明提供的一种以5,10‑[1,2]苯吩嗪衍生物为核心的化合物具有给电子特性,具有合适的HOMO/LUMO值和较高的三线态能量值,可以用于制备高性能有机EL元件。
Description
技术领域
本发明属于有机电致发光材料技术领域,涉及一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物及其应用。
背景技术
随着信息时代的来临,人机界面新型显示器的研究越来越引起人们的重视,特别是各类平板显示器件技术。有机电致发光(Organic Light Emitting Diodes,OLED)属于一种新型光电信息技术,其作为一种自发光的电子元件,OLED发光机理是在直流电场的作用下,借助有机半导体功能材料将电能直接转化为光能。OLED发光色彩可为单独的红、绿、蓝、黄光或者是组合白光。OLED发光显示技术的最大特点在于超薄、响应速度快、超轻量、面发光及柔性显示,可用于制造单色或全色显示器,还可以制作照明、显示产品或液晶显示器的背光源。OLED发光显示技术被认为是一种可以替代液晶显示器的新型平板显示器件,成为近年来新材料及显示技术领域研究开发的热点。随着有机电致发光器件结构不断优化,逐步形成了多功能层级结构,器件的效率和稳定性得到了长足的进步。
有机电致发光器件中的空穴注入层、空穴传输层、电子注入层、电子传输层主要用于降低电极和发光层之间的势垒,提高空穴和电子的注入率和传输率,从而降低器件的功耗,提高器件的发光效率和寿命。有机电致发光器件所选用的材料和器件结构直接决定了器件的效率高低和使用寿命的长短。CN108315010B公开了下式所示的二苯并吩嗪作为磷光材料,特别是室温磷光材料的用途该发明还涉及使用二苯并吩嗪作为磷光材料的有机电致发光器件;二苯并吩嗪作为一种纯有机的、不含重原子的氮杂环室温磷光材料,有可能实现一种新型的高效直接激子利用的纯有机电致磷光材料。但CN108315010B所公开的化合物仅作为磷光材料功能单一,因其结构不够稳定,难以减少因分子聚集而引起的猝灭和分子振动,所制备的有机电致发光器件性能难以满足市场要求。
提供一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物,具有给电子特性,具有合适的HOMO/LUMO值和较高的三线态能量值,能极大改善有机电致发光器件的器件性能。其对有机电致发光元件制造和有机电致发光显示技术发展,具有重要价值。
发明内容
本发明的目的在于提供一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物,作为空穴传输材料或发光材料应用到有机电致发光器件中,改善有机电致发光器件的器件性能。
基于上述目的,本申请通过提供一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物及其应用来解决该领域中的这种需要。
本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物,由于其特有的刚性和空间立体结构,可以有效的抑制π-π堆积,减少因分子聚集而引起的猝灭和分子振动,分子结构更加稳定。该化合物分子中的氮原子有别于C、Si、P原子的吸电子特性,母核结构中由于两个N原子的存在而具有胺基性质,可以有效传递空穴,进一步并吖啶环或并咔唑环可以提高母核结构的空穴传输能力,在此基础上引入胺基、咔唑基等给电子基团,构筑成具有典型空穴传输性能的材料。该类材料具有合适的分子前线轨道能级和较高的三线态能量(T1),可用作空穴传输材料和发光材料,改善有机电致发光器件的器件性能,具有广泛的应用市场前景。
一方面,本发明提供了一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物,其结构通式如式(I)所示:
其中X为单键或CR1R2,R1、R2独立的选自甲基;L为芳基;D为典型给电子基团;所述典型给电子基团选自取代或未被取代的胺基、取代或未被取代的咔唑基、取代或未被取代的吩噁嗪基、取代或未被取代的吖啶基、取代或未被取代的10H螺[吖啶-9,9’-芴]基、取代或未被取代的10H螺[吖啶-9,9’-呫吨]基、取代或未被取代的5-苯基-5,10-二氢吩嗪基、取代或未被取代的10H-吩噻嗪基中的一种。
优选地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,所述L为芳基,所述芳基为苯基、萘基、蒽基、芘基中的一种。
进一步地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,其结构通式如式(Ⅱ)或式(Ⅲ)所示:
进一步地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,所述D选自式(1)-(7)中任一项所示的结构:
具体地,所述Ar1、Ar2表示为苯基、联苯基、咔唑基、呋喃基中的一种;所述R1和R2表示为甲基、乙基、叔丁基、苯基、联苯基、咔唑基、呋喃基中的一种。
进一步地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,为以下化合物1-18中任一所述的具体结构:
进一步地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,为以下化合物19-41中任一所述的具体结构:
进一步地,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物中,为以下化合物42-47中任一所述的具体结构:
本发明提供了一系列以5,10-[1,2]苯吩嗪衍生物为核心的化合物,采用5,10-[1,2]苯吩嗪衍生物为核心的母核,进一步引入胺基、咔唑基等给电子基团,所构筑的化合物具有典型的给电子特性。本发明提供的化合物经过T1能级以及HOMO、LUMO能级测试,发现其性能突出,适合作为空穴传输材料或发光材料使用。本发明提供的化合物作为空穴传输材料或发光材料制得的有机电致发光器件经过性能测试发现其性能优良,在提高器件的发光效率、亮度等光电性能均有良好的表现。由此本发明进一步请求保护含本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物的有机电致发光材料;一种有机电致发光元件,包括阳极和阴极,以及位于所述阳极和阴极之间的至少含有空穴传输层、发光层、电子传输层,所述空穴传输层或发光层中的至少一种,含上述的有机电致发光材料;具体地,发光层为磷光器件、荧光器件、热活性延迟荧光器件中的任一种。并请求保护上述有机电致发光材料,或有机电致发光元件在有机电致发光显示中的应用。
本发明与现有技术相比具有以下有益效果或者优点:
本发明提供了多种以5,10-[1,2]苯吩嗪衍生物为核心的化合物,并给出了所述以5,10-[1,2]苯吩嗪衍生物为核心的化合物的合成方法。本发明提供的以5,10-[1,2]苯吩嗪衍生物为给体的化合物经过给电子基团进一步修饰构筑成具有典型空穴传输性质的结构,具有合适的HOMO/LUMO值和较高的三线态能量值,可以用于制备高性能有机EL元件。本发明通过空间立体结构的加入,使得以5,10-[1,2]苯吩嗪衍生物为核心的化合物具有较高的热稳定性,可显著提高发光器件的发光稳定性,适合作为空穴传输材料和发光层材料使用,在OLED发光器件及显示装置上具有广阔的应用前景。
附图说明
图1为本发明实施例中提供的一种有机电致发光元件的结构示意图。
附图标记说明:1为衬底,2为阳极层,3为空穴注入层,4为第一空穴传输层,5为第二空穴传输层,6为发光层,7为空穴阻挡层,8为电子传输层,9为电子注入层,10为阴极层。
具体实施方式
下面,结合实施例对本发明的技术方案进行说明,但是,本发明并不限于下述的实施例。
为了使本领域技术人员更好地理解本发明的技术方案能予以实施,下面结合具体实施例和附图对本发明作进一步说明,但所举实施例不作为对本发明的限定。
下述各实施例中所述实验方法和检测方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可在市场上购买得到。
实施例1
本实施例提供了化合物1、化合物2、化合物3、化合物30、化合物37、化合物42,及所涉及中间体的合成方法及过程。
(1)中间体1-3的合成
在三口瓶中依次加入300g中间体1-2,1170.5g中间体1-1,1004.1g碳酸钾,8L甲苯,通入氮气置换反应瓶中的空气后加入34.5g碘化亚铜,32.8g 1,10-邻菲咯啉,将反应液升温至110℃回流搅拌反应8h。降至室温后将反应液水洗至中性,有机相用无水硫酸钠干燥后过硅胶柱纯化得337.8g中间体1-3,收率62.7%。
在三口瓶中依次加入200g中间体1-3,99.5g中间体1-4,3L甲苯,通氮气置换反应瓶中的空气后加入16.6g 1,1’-双(二苯基膦)二茂铁,6.7g醋酸钯,86.2g叔丁醇钠,加热至回流搅拌反应6h。降温至室温后水洗至中性,常压蒸馏除去甲苯。所得固体经过硅胶柱纯化,得177.6g中间体1-5,收率73.2%。
在三口瓶中依次加入170g中间体1-5,2L四氢呋喃,降温至-78℃后通氮气置换反应瓶中的空气。将629.3mL 3.0M甲基溴化镁的2-甲基四氢呋喃溶液缓慢滴加到溶液中,升温至室温搅拌反应12h后加入蒸馏水淬灭反应,加入甲苯萃取。有机相水洗至中性后用无水硫酸镁干燥,减压浓缩后过硅胶柱纯化后得95.4g中间体1-6,收率56.1%。
在通氮气置换后得三口瓶中依次加入90g中间体1-6,1L多聚磷酸,加热至60℃搅拌反应8h后降至室温,在搅拌条件下缓慢倒入3L冰水中并持续搅拌0.5h。析出的固体过滤后将滤饼溶于甲苯,水洗至中性,然后无水硫酸钠干燥。将溶液浓缩后过硅胶柱纯化,重结晶得57.9g中间体1,收率67.3%。
在三口瓶中依次加入100g中间体1-3,41.8g中间体2-1,1.5L甲苯,通氮气置换反应瓶中的空气后加入8.3g 1,1’-双(二苯基膦)二茂铁,3.4g醋酸钯,43.1g叔丁醇钠,加热至回流搅拌反应6h。降温至室温后水洗至中性,常压蒸馏除去甲苯。所得固体经过硅胶柱纯化,得87.0g中间体2-2,收率76.3%。
三口瓶中依次加入85g中间体2-2,61.6g碳酸钾,6.8g特戊酸,1LN-甲基吡咯烷酮。通氮气置换反应瓶中的空气,加入2.5g醋酸钯,20.0mL 30%三叔丁基膦的甲苯溶液,加热至128-130℃反应6h后降温至室温。反应液中加入3L水搅拌析出固体,过滤后滤饼溶于甲苯中水洗至中性,无水硫酸钠干燥后减压蒸馏浓缩过硅胶柱纯化,重结晶得60.6g中间体2,收率78.7%。
(2)化合物1的合成
在三口瓶中依次加入10g中间体2,11.2g中间体1-1,7.8g碳酸钾,200mL甲苯,通入氮气置换反应瓶中的空气后加入0.41g溴化亚铜,0.52g 1,10-邻菲咯啉,将反应液升温至110℃回流搅拌反应8h。降至室温后将反应液水洗至中性,有机相用无水硫酸钠干燥后过硅胶柱纯化得14.0g化合物1,收率82.2%。
1H NMR(400MHz,CDCl3)δ8.23(d,J=8.0,2H),8.21(d,J=8.0,1H),8.12(s,1H),7.88(d,J=6.4,2H),7.91(d,J=6.4,2H),7.52-7.57(m,6H),7.13-7.19(m,8H),6.96(d,J=7.2,4H)。
(3)化合物2的合成
在三口瓶中依次加入10g中间体2,11.2g中间体1-1,7.8g碳酸钾,200mL甲苯,通入氮气置换反应瓶中的空气后加入0.41g溴化亚铜,0.52g 1,10-邻菲咯啉,将反应液升温至110℃回流搅拌反应8h。降至室温后将反应液水洗至中性,有机相用无水硫酸钠干燥后过硅胶柱纯化得13.4g化合物2,收率78.5%。
1H NMR(400MHz,CDCl3)δ8.21(d,J=8.0,1H),8.12(s,1H),7.76(d,J=6.4,2H),7.61(d,J=6.8,1H),7.51(t,J=6.8,1H),7.42(d,J=6.4,2H),7.19-7.23(m,5H),7.15(s,1H),7.04-7.10(m,8H),6.95-7.00(m,6H)。
(4)化合物3的合成
在三口瓶中依次加入10g中间体2,16.7g中间体3-1,7.8g碳酸钾,200mL甲苯,通入氮气置换反应瓶中的空气后加入0.41g溴化亚铜,0.52g 1,10-邻菲咯啉,将反应液升温至110℃回流搅拌反应8h。降至室温后将反应液水洗至中性,有机相用无水硫酸钠干燥后过硅胶柱纯化得16.5g化合物3,收率75.9%。
1H NMR(400MHz,CDCl3)δ8.21(d,J=8.0,1H),8.12(s,1H),7.97(d,J=6.8,2H),7.73(d,J=6.4,2H),7.61(d,J=6.8,1H),7.57(d,J=6.8,2H),7.51(t,J=6.8,1H),7.45(t,J=6.8,2H),7.40(d,J=6.4,2H),7.32(t,J=6.8,2H),7.15-7.22(m,8H),7.09(d,J=6.8,4H),6.94-7.00(m,6H)。
(5)化合物30的合成
中间体30-1可参考上述中间体1-3的合成方法得到。三口瓶中依次加入10g中间体1,10.9g中间体30-1,5.0g叔丁醇钠,200mL甲苯,通氮气置换反应瓶中的空气,加入0.3g醋酸钯,2.4mL 30%三叔丁基膦的甲苯溶液,加热至回流反应6h。降温至室温后水洗至中性,无水硫酸钠干燥后过硅胶柱纯化,重结晶得12.3g化合物30,收率72.6%。
1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.36-7.40(m,4H),7.21-7.26(m,6H),7.13-7.17(m,5H),7.02-7.08(m,6H),6.95(d,J=6.8,4H),2.37(s,6H),1.62(s,6H)。
(6)化合物37的合成
中间体37-1可参考上述中间体1-3的合成方法得到。三口瓶中依次加入10g中间体1,15.1g中间体37-1,5.0g叔丁醇钠,200mL甲苯,通氮气置换反应瓶中的空气,加入0.3g醋酸钯,2.4mL 30%三叔丁基膦的甲苯溶液,加热至回流反应6h。降温至室温后水洗至中性,无水硫酸钠干燥后过硅胶柱纯化,重结晶得15.4g化合物37,收率75.2%。
1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.38-7.43(m,4H),7.30-7.35(m,4H),7.19-7.26(m,10H),7.13-7.16(m,5H),7.02-7.10(m,8H),6.94(d,J=6.8,4H),1.60(s,6H)。
(7)化合物42的合成
中间体42-1可参考上述中间体1-3的合成方法得到。在三口瓶中依次加入10g中间体2,12.6g中间体42-1,7.8g碳酸钾,200mL甲苯,通入氮气置换反应瓶中的空气后加入0.41g溴化亚铜,0.52g 1,10-邻菲咯啉,将反应液升温至110℃回流搅拌反应8h。降至室温后将反应液水洗至中性,有机相用无水硫酸钠干燥后过硅胶柱纯化得14.1g化合物42,收率77.3%。
1H NMR(400MHz,CDCl3)δ8.21(d,J=8.0,1H),8.12(s,1H),7.79(d,J=6.4,2H),7.61(d,J=6.8,1H),7.51(t,J=6.8,1H),7.38(d,J=6.4,2H),7.14-7.21(m,8H),7.09(d,J=6.8,4H),6.95-7.00(m,6H),1.63(s,6H)。
实施例2
本实施例提供了以5,10-[1,2]苯吩嗪衍生物为核心的化合物的性能验证,具体包括T1能级以及HOMO、LUMO能级测试。
对实施例1提供的部分化合物及现有材料分别进行T1能级以及HOMO、LUMO能级测试,最高分子占有轨道(HOMO)和最低分子未占有轨道(LUMO)三线态能量(T1)为模拟计算所得数据,计算方法采用B3LYP杂化泛函,基组为6-31G(d,p),测试结果如表1所示。
表1,以5,10-[1,2]苯吩嗪衍生物为核心的化合物性能测试结果
化合物 | HOMO(eV) | LUMO(eV) | T1(eV) |
化合物1 | -5.344 | -0.902 | 3.186 |
化合物2 | -5.031 | -0.763 | 2.984 |
化合物3 | -5.045 | -0.927 | 2.971 |
化合物16 | -5.127 | -0.831 | 2.942 |
化合物30 | -4.938 | -0.594 | 2.996 |
化合物37 | -4.810 | -0.689 | 2.912 |
化合物40 | -4.936 | -0.702 | 2.963 |
化合物41 | -5.015 | -0.812 | 2.816 |
化合物42 | -4.877 | -0.894 | 2.810 |
化合物47 | -4.861 | -0.684 | 2.953 |
HT-2 | -5.270 | -2.091 | / |
BD01 | -4.75 | -1.61 | 2.63 |
HT-2和BD01为现有材料,其结构如下所示:
由表1可得,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物具有较高的三线态能量和较合适的HOMO/LUMO,在OLED器件中有利于载流子的传输和能量的转移,这些化合物可以作为空穴传输材料使用,也可以作为发光材料使用。基于上述数据测试结果,本领域内技术人员易于知晓,在没有特定限制的情况下,上述有机电致发光器件可以是磷光器件、荧光器件,也可以是热活性延迟荧光(TADF)材料器件。基于上述数据测试结果,本领域内技术人员易于知晓,本发明提供的以5,10-[1,2]苯吩嗪衍生物为核心的化合物在应用于OLED器件后,可以有效地提高器件的发光效率及使用寿命等性能。
实施例3
本实施例提供了部分以5,10-[1,2]苯吩嗪衍生物为核心的化合物为例,将其作为发光材料和/或空穴传输材料应用到有机电致发光器件中,以验证其所取得的优异效果。
本实施例通过器件实施例1~10和器件对比例1~2的器件性能详细说明本发明的OLED材料应用在器件中的优异效果。本发明器件实施例1~10以及器件对比例1~2的制作工艺相同,并且采用了相同的玻璃基板和电极材料,电极材料膜厚也保持一致,所不同的是第二空穴传输层材料或发光层中的主体材料做了调整,具体如下。
器件对比例1
器件对比例1提供了一种有机电致发光器件,其具体结构如图1所示,包括依次层叠设置的衬底1、阳极层2、空穴注入层3、第一空穴传输层4、第二空穴传输层5、发光层6、空穴阻挡层7、电子传输层8、电子注入层9和阴极层10。
其中,衬底1为0.7mm厚的玻璃基板,阳极层2材料选择具有高公函数的铟锡氧化物(ITO),空穴注入层3材料选择HAT-CN,厚度为5nm;第一空穴传输层4(HTL1)材料选择HT-1,厚度为60nm;第二空穴传输层5(HTL2)材料选择HT-2,厚度为15nm;发光层6使用BD01作为发光材料,以BH1作为主体材料,掺杂质量比为3%,厚度为30nm;空穴阻挡层7(HBL)的材料选择HB1,厚度为10nm;电子传输层8(ETL)的材料选择ET-1,厚度为35nm;电子注入层9的材料选择Liq,厚度为2nm;阴极层的材料选择Al,厚度为100nm。
器件中各功能层所使用基本材料结构式如下:
上述有机电致发光器件的具体制备步骤如下:
1)清洗透明玻璃基板上的ITO阳极,分别用去离子水、丙酮、乙醇各超声清洗20分钟,然后进行氧气氛围下等离子(Plasma)处理5分钟;
2)在ITO阳极层上,通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN,厚度为5nm,这层作为空穴注入层;
3)在空穴注入层上通过真空蒸镀方式蒸镀空穴传输材料HT-1,厚度为60nm,该层作为第一空穴传输层;
4)在第一空穴传输层HT-1上通过真空蒸镀方式蒸镀空穴传输材料HT-2,厚度为15nm,这层作为第二空穴传输层;
5)在第二空穴传输层上,通过真空蒸镀方式共蒸镀发光层,使用BD01作为发光材料,BH1作为主体材料,掺杂质量比为3%,厚度为30nm;
6)在发光层之上,通过真空蒸镀的方式蒸镀空穴阻挡材料HB1,厚度为10nm,这一层作为空穴阻挡层;
7)在空穴阻挡层上,通过真空蒸镀的方式蒸镀电子传输材料ET-1,厚度为35nm,这一层作为电子传输层;
8)在电子传输层上,通过真空蒸镀的方式蒸镀电子注入材料Liq,厚度为2nm,这一层作为电子注入层;
9)在电子注入层上,通过真空蒸镀的方式蒸镀阴极Al,厚度为100nm,该层作为阴极导电电极使用。
器件对比例2
与器件对比例1相同,不同之处:将CBP作为主体材料替代BH1,将GD02作为发光材料替代BD01。
器件实施例1
与器件对比例1相同,不同之处:将化合物2作为第二空穴传输层材料替代HT-2。
器件实施例2
与器件对比例1相同,不同之处:将化合物16作为第二空穴传输层材料替代HT-2。
器件实施例3
与器件对比例1相同,不同之处:将化合物27作为第二空穴传输层材料替代HT-2。
器件实施例4
与器件对比例1相同,不同之处:将化合物34作为第二空穴传输层材料替代HT-2。
器件实施例5
与器件对比例1相同,不同之处:将化合物40作为第二空穴传输层材料替代HT-2。
器件实施例6
与器件对比例1相同,不同之处:将化合物41作为第二空穴传输层材料替代HT-2。
器件实施例7
与器件对比例1相同,不同之处:将化合物47作为第二空穴传输层材料替代HT-2。
器件实施例8
与器件对比例2相同,不同之处:将化合物1作为主体材料替代CBP。
器件实施例9
与器件对比例2相同,不同之处:将化合物3作为主体材料替代CBP。
器件实施例10
与器件对比例2相同,不同之处:将化合物36作为主体材料替代CBP。
本发明器件实施例1~10、器件对比例1~2所制备的不同器件构成成分,具体如表2所示。
表2,各组有机电致发光器件构成成分对比表
将各组有机电致发光器件用公知的驱动电路将阴极和阳极连接起来,通过标准的方法,采用Keithley2400电源结合PR670光度计测试OLED器件的电压-效率-电流密度关系,具体测试结果如表3所示。
表3,各组有机电致发光器件性能测试结果
由表3可知,本发明提供的化合物作为发光材料和第二空穴传输层材料应用到OLED发光器件中,性能优良。如器件实施例3中的化合物27作为第二空穴层材料与器件对比例1中的HT-2相比,器件发光效率得到了显著的提高,其发光效率为8.53cd/A,6V电压下亮度达到了2369cd/m2;器件实施例9中的化合物3作为磷光主体材料与器件对比例2中的CBP相比,器件发光效率得到了显著的提高,其发光效率为60.63cd/A,6V电压下亮度达到了6230cd/m2。可见选用本发明的化合物作为OLED器件的主体材料或第二空穴传输层材料,对比现有材料应用的OLED发光器件,器件的发光效率、亮度等光电性能均有良好的表现,在OLED器件的应用上具有很大的应用价值和商业前景,具有良好的产业化前景。
如上所述,即可较好地实现本发明,上述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种改变和改进,均应落入本发明确定的保护范围内。
Claims (5)
1.一种以5,10-[1,2]苯吩嗪衍生物为核心的化合物,其特征在于,为以下化合物1-47中任一所述的具体结构:
2.一种有机电致发光材料,其特征在于,含有权利要求1所述的以5,10-[1,2]苯吩嗪衍生物为核心的化合物。
3.一种有机电致发光元件,包括阳极和阴极,以及位于所述阳极和阴极之间的至少含有空穴传输层、发光层、电子传输层,其特征在于,所述空穴传输层或发光层中的至少一种,含权利要求2所述的有机电致发光材料。
4.根据权利要求3所述的有机电致发光元件,其特征在于,所述发光层为磷光器件、荧光器件、热活性延迟荧光器件中的任一种。
5.权利要求2所述的有机电致发光材料,或权利要求3所述的有机电致发光元件在有机电致发光显示中的应用。
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