CN113461550B - Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device - Google Patents
Compound and intermediate thereof and application of compound and intermediate thereof in organic electroluminescent device Download PDFInfo
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- CN113461550B CN113461550B CN202010241193.5A CN202010241193A CN113461550B CN 113461550 B CN113461550 B CN 113461550B CN 202010241193 A CN202010241193 A CN 202010241193A CN 113461550 B CN113461550 B CN 113461550B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 113
- 238000002347 injection Methods 0.000 claims abstract description 42
- 239000007924 injection Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 230000005525 hole transport Effects 0.000 claims abstract description 30
- 239000010410 layer Substances 0.000 claims description 79
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- 239000012044 organic layer Substances 0.000 claims description 23
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004305 biphenyl Chemical class 0.000 claims description 8
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 125000005567 fluorenylene group Chemical class 0.000 claims description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 3
- 125000004957 naphthylene group Chemical class 0.000 claims description 3
- 125000000843 phenylene group Chemical class C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000006836 terphenylene group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 230000015572 biosynthetic process Effects 0.000 description 55
- 238000003786 synthesis reaction Methods 0.000 description 55
- 238000001514 detection method Methods 0.000 description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000001704 evaporation Methods 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- -1 spirofluorenyl Chemical group 0.000 description 27
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 20
- 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 20
- 230000008020 evaporation Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000004949 mass spectrometry Methods 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 238000010898 silica gel chromatography Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000001308 synthesis method Methods 0.000 description 11
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- YDYIKNZEGGFAKG-UHFFFAOYSA-N 2-N,7-N-diethyl-9,9-dimethylfluorene-2,7-diamine Chemical compound CCNC(C=C1)=CC(C(C)(C)C2=C3)=C1C2=CC=C3NCC YDYIKNZEGGFAKG-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- FSSYNTJUYWSXFS-UHFFFAOYSA-N n-ethyl-4-[4-(ethylamino)phenyl]aniline Chemical compound C1=CC(NCC)=CC=C1C1=CC=C(NCC)C=C1 FSSYNTJUYWSXFS-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- ZEMODTUZIWTRPF-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(NCC)C=C1 ZEMODTUZIWTRPF-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000006749 (C6-C60) aryl group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000006761 (C6-C60) arylene group Chemical group 0.000 description 4
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- KCLWJZWBXNWRND-UHFFFAOYSA-N COCCOCCC(C=C(C=C1)N)=C1C(C=C1)=CC=C1N Chemical compound COCCOCCC(C=C(C=C1)N)=C1C(C=C1)=CC=C1N KCLWJZWBXNWRND-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)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)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 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 description 3
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 3
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000005580 triphenylene group Chemical group 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- LONBOJIXBFUBKQ-UHFFFAOYSA-N 2,7-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LONBOJIXBFUBKQ-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical group 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical group C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- QFUDENSTNNSGFG-UHFFFAOYSA-N 2,2',7'-tribromo-9,9'-spirobi[fluorene] Chemical compound C12=CC(Br)=CC=C2C2=CC=C(Br)C=C2C11C2=CC=CC=C2C2=CC=C(Br)C=C21 QFUDENSTNNSGFG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WNXNWOBGPRKOJF-UHFFFAOYSA-N 2-bromo-9,9-diphenylfluorene Chemical group C12=CC(Br)=CC=C2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 WNXNWOBGPRKOJF-UHFFFAOYSA-N 0.000 description 1
- CSFNUYPFWSRMET-UHFFFAOYSA-N 3-phenyl-n-(4-phenylphenyl)aniline Chemical group C=1C=CC(C=2C=CC=CC=2)=CC=1NC(C=C1)=CC=C1C1=CC=CC=C1 CSFNUYPFWSRMET-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NNOBZUFIEWMDHW-UHFFFAOYSA-N n-[2-(2-methoxyethoxy)ethyl]aniline Chemical compound COCCOCCNC1=CC=CC=C1 NNOBZUFIEWMDHW-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 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
-
- 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
Abstract
The invention relates to a compound and an intermediate thereof, and application of the compound in an organic electroluminescent device, wherein the compound has a structure shown in a formula I, and the compound is applied to the organic electroluminescent device, particularly used as a hole transport layer material or a hole injection layer material, so that the device has higher luminous efficiency and lower driving voltage, and is further applied to a display panel and a display device.
Description
Technical Field
The invention relates to the technical field of display, in particular to a compound and an intermediate thereof, and application of the compound and the intermediate in an organic electroluminescent device.
Background
Organic light-emitting diode (OLED) has the advantages of no need of backlight source for active light emission, high luminous efficiency, large visual angle, high response speed, large temperature application range, relatively simple production and processing technology, low driving voltage, small energy consumption, lighter and thinner flexible display and the like, and huge application prospect, and attracts attention of a plurality of researchers.
In the diode field, electron transport and hole transport are often involved, and the transport rates of hole transport and electron transport are generally different, which greatly affects the efficiency, service life, etc. of the diode.
In an OLED device, the choice of carrier transport layer can greatly affect the performance of light emission efficiency, driving voltage, device lifetime, etc. At present, the transmission performance of the hole transmission layer is far lower than that of the electron transmission layer, and the charge transmission balance of the device is difficult to realize. Also, the choice of the hole injection layer material is of great importance.
Accordingly, there is a need in the art to develop more types of higher performance OLED materials, particularly hole transporting materials and hole injecting materials, to improve device performance.
Disclosure of Invention
It is an object of the present invention to provide a compound which can be used in an organic electroluminescent device, particularly a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material, enabling a device having higher luminous efficiency and lower driving voltage.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a compound, which has a structure shown in a formula I;
in the formula I, the Ar 1 A substituent selected from a substituted or unsubstituted C6-C60 arylene group, the C6-C60 arylene group being selected from a C1-C30 aliphatic alkyl group or a C1-C30 aliphatic alkoxy group;
in the formula I, the Ar 2 、Ar 3 And Ar is a group 4 Each independently selected from a group shown in a formula II or a substituted or unsubstituted C6-C60 aryl, wherein the substituent of the C6-C60 aryl is selected from C1-C30 aliphatic alkyl or C1-C30 aliphatic alkoxy;
in formula II, the wavy line represents the bond of the group;
in the formula II, W is selected from C6-C60 arylene;
in formula II, the Ar 5 And Ar is a group 6 Each independently selected from C6-C60 aryl;
in the formula I, X, Y and Z are each independently selected from any one of substituted or unsubstituted C1-C30 aliphatic alkyl, substituted or unsubstituted C3-C30 cycloalkyl and substituted or unsubstituted C1-C30 aliphatic alkoxy, and the substituent of the C1-C30 aliphatic alkyl, the C3-C30 cycloalkyl or the C1-C30 aliphatic alkoxy is selected from C6-C60 aryl;
in the formula I, n is 0 or 1;
any hydrogen atom in formula I is replaced with deuterium or not replaced with deuterium.
Ar on the existing OLED analog compound 1 The N atoms at both ends are substituted by aromatic compounds, belonging to triarylamine compounds, the invention provides a compound shown in formula I, the compound Ar 1 One substituent group on N atoms at two ends is changed from an aromatic compound to X and Y (or X, Y and Z) shown in the invention, so that the HOMO and LOMO energy levels of the material are improved, and the material disclosed by the invention is used as a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material, and has higher luminous efficiency and lower driving voltage when being applied to an OLED device. The structure is changed, and simultaneously, the solubility of the material in the organic solvent, the film forming property of the residual organic material after the solvent is volatilized and the viscosity property of the material in the organic solvent are correspondingly changed, so that the material is more suitable for being prepared by a solution method when being used for preparing OLED devices.
In the present invention, "substituted or unsubstituted" means that a substituent may be substituted or unsubstituted on the group, for example, a substituted or unsubstituted C1-C30 aliphatic alkyl group means that a substituent may be substituted or no longer substituted on the C1-C30 aliphatic alkyl group. The number of substituents is not limited as long as the number of substituents is within the maximum substitutable number, and when two or more substituents are simultaneously substituted on the same group, the two or more substituents may be the same or different. The invention relates to the same expression mode and has the same meaning.
In the present invention, the number of carbon atoms of the C6-C60 arylene group may be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, etc.; the number of carbon atoms of the C6-C60 aryl group may be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, etc.; the number of carbon atoms of the C1-C30 aliphatic alkyl group may be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, etc.; the number of carbon atoms of the C1-C30 aliphatic alkoxy group may be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, etc.; the number of carbon atoms of the C3-C30 cycloalkyl group may be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, etc.
Preferably, the compound has a structure represented by formula III;
in formula III, the X, Y, ar 1 、Ar 2 And Ar is a group 3 Each independently has the same meaning as in formula I.
Preferably, the Ar 1 Selected from phenyl, naphthyl, anthryl, phenanthryl, 9-dialkyl substituted fluorenyl, spirofluorenyl, carbazolyl, dibenzothienyl, dibenzofuranyl, indolocarbazolyl, indenocarbazolyl, biphenyl, binaphthyl, bianthrenyl, dibenzoyl, terphenyl, triphenylene, fluoranthryl, benzophenanthrylOr hydrogenated benzanthracene groups.
Preferably, the Ar 2 、Ar 3 And Ar is a group 4 Each independently selected from the group represented by formula II, or each independently selected from any one or at least two of phenyl, naphthyl, anthryl, phenanthryl, 9-diphenyl substituted fluorenyl, 9-dialkyl substituted fluorenyl, biphenyl, binaphthyl, bianthrenyl, binaphthyl, terphenyl, triphenylene, fluoranthryl, benzophenanthryl or hydrogenated benzanthraceyl.
Preferably, when n is 1, the Ar 2 、Ar 3 And Ar is a group 4 At least one (e.g., one, two, three, or four, etc.) of which is selected from the group represented by formula II; when n is 0, the Ar 2 And Ar is a group 3 At least one (e.g., one, two, three, or four, etc.) of which is selected from the group represented by formula II.
The invention preferably has at least one arylamine group shown in the formula II, so that the compound at least contains three arylamine structures, the structure enables conjugation of molecules to be large, eg between corresponding HOMO and LUMO to be small, and HOMO to be improved, so that energy level difference between the material serving as a hole injection material and ITO is small, hole injection is facilitated, light-emitting efficiency of the device can be further improved, and driving voltage is reduced.
Preferably, in formula III, the Ar 2 And Ar is a group 3 At least one of which is selected from the group represented by formula II.
Preferably, W is selected from any one of phenylene, biphenylene, naphthylene, 9-diphenyl substituted fluorenylene or 9, 9-dialkyl substituted fluorenylene, spirobifluorenylene, and terphenylene.
Preferably, the Ar 5 And Ar is a group 6 Each independently selected from any one of phenyl, naphthyl, anthryl, phenanthryl, 9-diphenyl substituted fluorenyl, 9-dialkyl substituted fluorenyl, biphenyl, binaphthyl, bianthrenyl, dibenzoyl, terphenyl, triphenylene, fluoranthryl, benzophenanthryl, or hydrogenated benzanthrenyl.
Preferably, each of X, Y and Z is independently selected from a group of formula IV or a C3-C30 cycloalkyl group;
in formula IV, the L 1 From C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) aliphatic alkyl, said L 2 An aliphatic alkyl group selected from C1 to C6 (e.g., C2, C3, C4, C5, C6, etc.);
in formula IV, m is an integer of 0 to 6, for example, 1, 2, 3, 4, 5, etc.;
in formula IV, the wavy line represents the bond of the group, i.e. formula IV to L 1 Is attached to the N atom in formula I.
Preferably, the compound has any one of the structures shown in the following P-1 to P-182:
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ar in the compound shown in the formula I 2 、Ar 3 、Ar 4 When n=1, the synthetic route is represented as follows:
wherein Ar is 1 、Ar 3 The structures represented by X and Y are as described in the above part of the specification, and Z represents chlorine, bromine and iodine.
The compounds shown in V and M-2 are subjected to carbon-nitrogen coupling reaction to generate the compound shown in the formula I.
It is a second object of the present invention to provide an intermediate for a compound according to one of the preparation purposes, said intermediate having the following structure:
in formula V, the compounds X, Y, Z and Ar 1 All have the same meaning as in formula I.
It is a further object of the present invention to provide the use of a compound according to one of the objects, said compound being useful in an organic electroluminescent device.
Preferably, the compound is used as a hole transport layer material or a hole injection layer material of an organic electroluminescent device.
A fourth object of the present invention is to provide an organic electroluminescent device comprising an anode layer and a cathode layer, and an organic layer provided between the anode layer and the cathode layer, the organic layer containing the compound according to one of the objects.
Preferably, the organic layer includes a hole injection layer, and the hole injection layer contains the compound of one of the purposes.
Preferably, the organic layer includes a hole transport layer containing the compound of one of the purposes.
The fifth object of the present invention is to provide a display panel comprising the organic electroluminescent device of the fourth object.
A sixth object of the present invention is to provide a display device including the organic electroluminescent device of fourth object or the display panel of fifth object.
Compared with the prior art, the invention has the following beneficial effects:
the compound provided by the invention can be applied to an organic electroluminescent device, particularly used as a Hole Injection Layer (HIL) material or a Hole Transport Layer (HTL) material, can enable the device to have higher luminous efficiency and lower driving voltage, and is more suitable for being prepared by a solution method when being used for preparing an OLED device.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The following synthesis examples are provided by way of example for specific compounds, but the present invention is not limited to the specific synthesis methods described below, and one skilled in the art can select the synthesis methods according to the prior art.
Synthesis example 1P-1 Synthesis
(1) Synthesis of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine
To a 500 ml three-necked flask, 12.1 g (0.1 mol) of N-ethylaniline, 300 ml of toluene and 27 g (0.1 mol) of ferric trichloride hexahydrate were added, the mixture was stirred and heated to 80℃for reaction for 4 hours, the temperature was lowered, water was added, the organic layer was washed to be neutral, and the mixture was separated by silica gel column chromatography and petroleum ether: ethyl acetate=9: 1 to obtain 8.6g of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine with a yield of 71.67%.
Mass spectrum detection is carried out on the obtained product N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, and the molecular m/z is determined as follows: 240.
the nuclear magnetism of the obtained product N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.50(m，4H)，δ6.53(m，4H)，δ3.62(s，2H)，δ3.45(m，4H)，δ1.29(t，6H)。
(2) Synthesis of P-1
500 ml three-port flask, nitrogen protection, adding 80 ml dry toluene, 2.4 g (0.01 mol) N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, 3.45 g (0.022 mol) bromobenzene, 0.0575 g (0.0001 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.4 g (0.0002 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 2.3 g (0.024 mol) of sodium tert-butoxide, heating to reflux reaction for 4 hours, cooling, adding water, concentrating the organic layer to dryness, separating by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 (volume ratio) to give 3.6 g of the compound represented by P-1 in 91.8% yield.
Mass spectrum detection is carried out on the compound shown in the P-1, and the molecular m/z is determined as follows: 392.
the nuclear magnetic resonance detection was performed on the compound shown in P-1, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.55(m，4H)，δ7.45～7.38(m，6H)，δ7.35(m，6H)，δ7.08(m，2H)，δ3.59～3.47(m，4H)，δ1.15(t，6H)。
synthesis of Synthesis example 2P-5
The synthesis method was the same as that of P-1 in example 1 except that bromobenzene was replaced with 2-bromo-9, 9-diphenylfluorene in the same amount to give compound P-5.
Mass spectrometry detection was carried out on the compound shown as P-5, and the molecular m/z is determined as follows: 872.
the nuclear magnetic resonance detection was performed on the compound shown in P-5, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ8.00(m，2H)，δ7.92(m，2H)，δ7.87(d，2H)，δ7.65(d，2H)，δ7.55(m，4H)，δ7.41～7.32(m，6H)，δ7.29～7.14(m，16H)，δ7.11(m，8H)，δ3.62～3.46(m，4H)，δ1.15(t，6H)。
synthesis of Synthesis examples 3 to P to 15
The synthesis method is the same as that of P-1 in example 1, except that bromobenzene is replaced with the same amount ofCompound P-15 is obtained.
Mass spectrometry detection was carried out on the compound shown as P-15, and the molecular m/z is determined as follows: 896.
the nuclear magnetic resonance detection was performed on the compound shown by P-15, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ8.20(m，8H)，δ7.66(m，4H)，δ7.55(m，12H)，δ7.46～7.34(m，18H)，δ3.36～3.22(m，4H)，δ1.15(t，6H)。
synthesis of Synthesis examples 4 to P to 19
The synthesis method was the same as that of P-1 in example 1 except that bromobenzene was replaced with equal amounts of 4-bromotriphenylamine to give compound P-19.
Mass spectrometry detection was carried out on the compound shown as P-19, and the molecular m/z is determined as follows: 726.
the nuclear magnetic resonance detection was performed on the compound shown by P-19, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.57(m，4H)，δ7.38(m，4H)，δ7.26(m，8H)，δ7.15(s，8H)，δ7.06(m，8H)，δ7.00(m，4H)，δ3.63～3.48(m，4H)，δ1.15(t，6H)。
synthesis of Synthesis examples 5 to P-23
The synthesis method is the same as that of P-1 in example 1, except that bromobenzene is replaced with the same amount ofCompound P-23 is obtained.
Mass spectrometry detection was carried out on the compound shown as P-23, and the molecular m/z is determined as follows: 958.
the nuclear magnetic resonance detection was performed on the compound shown by P-23, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.88(d，4H)，δ7.56(m，4H)，δ7.49(m，4H)，δ7.38(m，4H)，δ7.28～7.16(m，12H)，δ7.11(m，8H)，δ7.02(m，4H)，δ3.61～3.52(m，4H)，δ1.70(s，12H)，δ1.15(t，6H)。
synthesis of Synthesis examples 6P-34
The synthesis method comprises the following steps:
(1) Into a 250 ml autoclave, 3.52 g (0.01 mol) of 2, 7-dibromo-9, 9-dimethylfluorene, 4.5 g (0.1 mol) of ethylamine, 20 ml of toluene, 50 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide, 5.52 g (0.04 mol) of potassium carbonate and nitrogen were added, after replacement, the mixture was heated in a sealed manner to 100 ℃ for reaction for 8 hours, cooled, water was added, the organic layer was washed with water to neutrality and concentrated to dryness, and the mixture was separated by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 to obtain 1.61 g of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine with a yield of 57%.
Mass spectrum detection is carried out on the obtained product N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined as follows: 280.
the nuclear magnetism of the obtained product N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.77(d，2H)，δ6.91(d，2H)，δ6.66(m，2H)，δ3.66(s，2H)，δ3.45(m，4H),δ1.71(s，6H)，δ1.28(t，6H)。
(2) 250 ml three-port flask, nitrogen protection, 100 ml dry toluene, 2.8 g (0.01 mol) N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine as indicated in P-34-2, 3.45 g (0.022 mol) bromobenzene, 0.0575 g (0.0001 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.4 g (0.0002 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 2.3 g (0.024 mol) of sodium tert-butoxide, heating and refluxing for reaction for 8 hours, cooling, adding water solution, washing an organic layer to be neutral, separating by silica gel column chromatography, and petroleum ether: ethyl acetate=9: 1 (volume ratio) to give 3.5 g of the compound represented by P-34 in a yield of 81%.
Mass spectrometry detection was carried out on the compound shown as P-34, and the molecular m/z is determined as follows: 432.
the nuclear magnetic resonance detection was performed on the compound shown by P-34, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.88(d，2H)，δ7.40(m，6H)，δ7.35(m，4H)，δ7.15(m，2H)，δ7.09(m，2H)，δ3.60～3.47(m，4H)，δ1.70(s，6H)，δ1.15(t，6H)。
synthesis of Synthesis example 7P-52
The synthesis was the same as that of P-34 in example 6 except that bromobenzene was converted to an equivalent amount of 4-bromo-triphenylamine to give compound P-52.
Mass spectrometry detection was performed on the compound shown as P-52 to determine that the molecular m/z is: 766.
the nuclear magnetic resonance detection was performed on the compound shown by P-52, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.80(d，2H)，δ7.33(d，2H)，δ7.15(m，8H)，δ7.06(m，10H)，δ7.03(m，8H)，δ6.95(m，4H)，δ3.60～3.44(m，4H)，δ1.68(s，6H)，δ1.14(t，6H)。
synthesis of Synthesis examples 8 to P to 55
Synthesis method the same as for P-34 in Synthesis example 6 except that bromobenzene was converted into an equivalent amountCompound P-55 is obtained.
Mass spectrometry detection was performed on the compound shown as P-55 to determine that the molecular m/z is: 918.
the compound shown as P-55 was subjected to nuclear magnetic resonance detection, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.88(d，2H)，δ7.55(m，8H)，δ7.45(d，2H)，δ7.39(m，8H)，δ7.26(m，8H)，δ7.17(d，2H)，δ7.11(m，8H)，δ7.02(m，4H)，δ3.64～3.53(m，4H)，δ1.70(s，6H)，δ1.14(t，6H)。
synthesis of examples 9P-67
(1) Synthesis of N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine
Synthetic method referring to the synthesis of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine in example 6, only the ethylamine was replaced with an equivalent mass of benzylamine to give N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine.
Mass spectrum detection is carried out on the obtained product N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined as follows: 404.
the nuclear magnetism of the obtained product N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.83(d，2H)，δ7.34～7.29(m，10H)，δ6.97(d，2H)，δ6.70(m，2H)，δ4.33(s，4H)，δ3.95(s，2H),δ1.71(s，6H)。
(2) Synthesis of P-67
Synthesis method referring to the method for synthesizing P-34 in example 6, N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was converted to N2, N7-dibenzyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine of equal mass, and bromobenzene was converted to bromobenzene of equal massTo obtain the compound shown as the formula P-67.
Mass spectrometry detection was carried out on the compound shown as P-67, and the molecular m/z is determined as follows: 1082.
the nuclear magnetic resonance detection was performed on the compound shown by P-67, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.79(d，4H)，δ7.72(d，2H)，δ7.52(d，2H)，δ7.50～7.43(m，6H)，δ7.39(m，2H)，δ7.33(m，4H)，δ7.26～7.14(m，18H)，δ7.03(m，8H)，δ6.95(m，4H)，δ4.35(s，2H),δ4.21(s，2H)，δ1.71(s，12H)。
synthesis of examples 10P-82
(1) Synthesis of N1, N4-diethylbenzene-1, 4-diamine
Synthetic method referring to the synthesis of N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine in example 6, only 2, 7-dibromo-9, 9-dimethylfluorene was converted into p-dibromobenzene of equivalent amount to give N1, N4-diethylbenzene-1, 4-diamine.
Mass spectrum detection is carried out on the obtained product N1, N4-diethylbenzene-1, 4-diamine, and the molecular m/z is determined as follows: 164.
the nuclear magnetism of the obtained product N1, N4-diethylbenzene-1, 4-diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ6.59(s，4H)，δ3.47(m，4H)，δ2.83(s，2H)，δ1.29(t，6H)。
(2) Synthesis of P-82
Synthesis method referring to the method for synthesizing P-34 in example 6, N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was converted to N1, N4-diethylbenzene-1, 4-diamine of equal mass, and bromobenzene was converted to bromobenzene of equal massTo obtain the compound shown as the formula P-82.
Mass spectrometry detection was carried out on the compound shown as P-82, and the molecular m/z is determined as follows: 1034.
the nuclear magnetic resonance detection was performed on the compound shown by P-82, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ8.11(m，2H)，δ7.91(m，2H)，δ7.87(d，2H)，δ7.54～7.49(m，4H)，δ7.45～7.36(m，10H)，δ7.35～7.29(m，4H)，δ7.25(m，2H)，δ7.17～7.11(m，14H)，δ7.09(m，4H)，δ3.39(m，2H)，δ3.33(m，2H)，δ1.70(s，12H)，δ1.15(t，6H)。
synthesis of Synthesis examples 11 and P-91
(1) Synthesis of N1, N3, N5-triethylbenzene-1, 3, 5-triamine
In a 250 ml autoclave, 3.15 g (0.01 mol) of 1,3, 5-tribromobenzene, 5.4 g (0.2 mol) of ethylamine, 20 ml of toluene, 50 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide, 8.28 g (0.06 mol) of potassium carbonate and nitrogen are added, and after replacement, the mixture is heated to 100 ℃ in a closed state and reacted for 8 hours, the temperature is reduced, the water is added, the organic layer is washed to be neutral, the mixture is concentrated to be dry, and the mixture is separated by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 to obtain 1.11 g of N1, N3, N5-triethylbenzene-1, 3, 5-triamine with a yield of 53.6%.
Mass spectrum detection is carried out on the obtained product N1, N3, N5-triethylbenzene-1, 3,5 triamine, and the molecular m/z is determined as follows: 207.
the nuclear magnetism of the obtained product N1, N3, N5-triethylbenzene-1, 3,5 triamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ5.26(s，3H)，δ3.47(m，6H)，δ3.35(s，3H)，δ1.29(t，9H)。
(2) Synthesis of the Compound shown as P-91:
250 ml three-port flask, nitrogen protection, 100 ml dry toluene, 2.07 g (0.01 mol) N1, N3, N5-triethylbenzene-1, 3, 5-triamine, 12.96 g (0.04 mol) 4-bromo-N, N-diphenylaniline, 0.115 g (0.0002 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.8 g (0.0004 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 3.46 g (0.036 mol) of sodium tert-butoxide, heating and refluxing for reaction for 8 hours, cooling, adding water solution, washing an organic layer to be neutral, separating by silica gel column chromatography, and petroleum ether: ethyl acetate: dichloromethane = 9:0.5:0.5 (volume ratio) elution gave 5.6 g of the compound represented by P-91 in 59.8% yield.
Mass spectrometry detection is carried out on the compound shown as P-91, and the molecular m/z is determined as follows: 936.
the nuclear magnetic resonance detection was performed on the compound shown by P-91, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.26(m，12H)，δ7.13(s，12H)，δ7.09(m，12H)，δ7.02(m，6H)，δ6.51(s，3H)，δ3.59(m，3H)，δ3.53(m，3H)，δ1.15(t，9H)。
synthesis of examples 12P-107
Synthetic method reference was made to the synthesis of P-55 in synthetic example 8 except that (1) the ethylamine was replaced with N-butylamine to give N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine.
Mass spectrum detection is carried out on the obtained product N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the molecular m/z is determined as follows: 336.
the nuclear magnetism of the obtained product N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.79(d，2H)，δ6.91(d，2H)，δ6.66(m，2H)，δ3.70(s，2H)，δ3.31(m，4H),δ1.71(s，6H)，δ1.49(m，4H),δ1.31(m，4H),δ0.90(t，6H)。
in the step (2), the step (2) was conducted with reference to Synthesis example 8, except that N2, N7-diethyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine was changed to N2, N7-di-N-butyl-9, 9-dimethyl-9H-fluorene-2, 7-diamine, and the mixture was reacted with a catalystChange to->The compound shown as P-107 is obtained.
Mass spectrometry detection was performed on the compound shown as P-107 to determine that the molecular m/z is: 1126.
the nuclear magnetic resonance detection was performed on the compound shown by P-107, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.88(d，2H)，δ7.77(m，8H)，δ7.56(m，8H)，δ7.51(m，8H)，δ7.43(m，4H)，δ7.38(m，8H)，δ7.17(s，8H)，δ6.53(d，2H)，δ6.15(m，2H)，δ3.95(t，4H)，δ1.70(s，6H)，δ1.49(m，4H)，δ1.32(m，4H)，δ0.91(t，6H)。
synthesis of examples 13 to P to 150
(1) Synthesis of N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine
500 ml three-necked flask, nitrogen protection, and 80 ml of dry toluene, 2.4 g (0.01 mol) of N, N ' -diethyl-1, 1' -biphenyl-4, 4' -dicarboxylic acidAmine, 1.57 g (0.01 mol) bromobenzene, 0.0575 g (0.0001 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.4 g (0.0002 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 1.44 g (0.015 mol) of sodium tert-butoxide, heating to 60 ℃ for 4 hours, cooling, adding water, concentrating an organic layer to dryness, separating by silica gel column chromatography, and petroleum ether: ethyl acetate = 15:1 (volume ratio) to obtain N4, N4 '-diethyl-N4-phenyl- [1,1' -biphenyl]1.22 g of 4,4' -diamine and a yield of 38.6%.
Mass spectrometry detection was performed on N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine to determine that the molecular m/z is: 316.
nuclear magnetic detection was performed on N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.57(m，2H)，δ7.51(m，2H)，δ7.44～7.30(m，6H)，δ7.07(m，1H)，δ6.52(m，2H)，δ3.60～3.49(m，3H)，δ3.47(m，2H)，δ1.29(t，3H)，δ1.15(t，3H)。
(2) Synthesis of P-150
500 ml three-necked flask, nitrogen protection, 200 ml of dry toluene, 3.16 g (0.01 mol) of N4, N4 '-diethyl-N4-phenyl- [1,1' -biphenyl were added]-4,4 '-diamine, 5.52 g (0.01 mol) N, N-di ([ 1,1' -biphenyl)]-4-yl) -4 '-bromo- [1,1' -biphenyl]-4-amine, 0.0575 g (0.0001 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.4 g (0.0002 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 1.44 g (0.015 mol) of sodium tert-butoxide, heating to reflux reaction for 8 hours, cooling, adding water solution, concentrating the organic layer to dryness, separating by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 (volume ratio) to give 5.92 g of the compound represented by P-150 in 75.1% yield.
Mass spectrometry detection is carried out on the compound shown by P-150, and the molecular m/z is determined as follows: 787.
the nuclear magnetic resonance detection was performed on the compound shown by P-150, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.73(m，4H)，δ7.53(m，12H)，δ7.47(m，5H)，δ7.40～7.29(m，17H)，δ7.03(m，1H)，δ3.61～3.47(m，4H)，δ1.15(t，6H)。
synthesis of examples 14 and P to 160
(1) Synthesis of N1- ([ 1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine
Synthetic method reference was made to the synthesis of N4, N4' -diethyl-N4-phenyl- [1,1' -biphenyl ] -4,4' -diamine in example 13, except that N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine was replaced with N1, N4-diethylbenzene-1, 4-diamine and bromobenzene was replaced with 4-bromobiphenyl to give N1- ([ 1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine.
Mass spectrometry detection is carried out on N1- ([ 1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine, and the molecular m/z is determined as follows: 316.
nuclear magnetic detection was performed on N1- ([ 1,1' -biphenyl ] -4-yl) -N1, N4-diethylbenzene-1, 4-diamine, and the data were resolved as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.77(m，2H)，δ7.57(m，2H)，δ7.51(m，2H)，δ7.41(m，1H)，δ7.36(m，2H)，δ7.08(m，2H)，δ6.95(m，2H)，δ3.59～3.41(m，4H)，δ3.21(s，1H)，δ1.29(t，3H)，δ1.15(t，3H)。
(2) Synthesis of P-160
Synthesis method referring to the synthesis of P-150 in example 13, N-di ([ 1,1 '-biphenyl ] -4-amine) was replaced with N- ([ 1,1' -biphenyl ] -4-yl) - [1,1 '-biphenyl ] -3-amine by replacing N4, N4' -diethyl-N4-phenyl- [1,1 '-biphenyl ] -4,4' -diamine with N1- ([ 1,1 '-biphenyl ] -4-yl) -N- (4' -bromo- [1,1 '-biphenyl ] -4-yl) - [1,1' -biphenyl ] -3-amine to obtain the compound shown as P-160.
Mass spectrometry detection was performed on the compound shown as P-160 to determine that the molecular m/z is: 787.
the nuclear magnetic resonance detection was performed on the compound shown by P-160, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.77(m，6H)，δ7.59～7.39(m，17H)，δ7.36(m，6H)，δ7.29(t，2H)，δ7.18(m，4H)，δ7.16(s，4H)，δ3.60～3.48(m，4H)，δ1.15(t，6H)。
synthesis of Synthesis examples 15 to P to 170
(1) Synthesis of N4, N4 '-bis (4-bromophenyl) -N4, N4' -diethyl- [1,1 '-biphenyl ] -4,4' -diamine
250 ml three-port flask, nitrogen protection, 100 ml dry toluene, 2.4 g (0.01 mol) N, N ' -diethyl-1, 1' -biphenyl-4, 4' -diamine, 18.9 g (0.08 mol) p-dibromobenzene, 0.115 g (0.0002 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.8 g (0.0004 mol) of toluene solution containing 10 percent of tri-tert-butyl phosphine, 3.84 g (0.04 mol) of sodium tert-butoxide, heating to 60 ℃ for 4 hours, cooling, adding water solution, washing an organic layer to be neutral, separating by silica gel column chromatography and petroleum ether elution to obtain N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl]1.9 g of 4,4' -diamine and a yield of 34.5%.
p-N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl]Mass spectrometric detection of 4,4' -diamine, determination of the molecular m/z as: 550, determining the molecular formula as C 28 H 26 Br 2 N 2 。
(2) Synthesis of P-170-1
500 ml three-necked flask, nitrogen protection, 200 ml dry toluene, 5.5 g (0.01 mol) N4, N4' -bis (4-bromophenyl) -N4, N4' -diethyl- [1,1' -biphenyl were added]-4,4'-Diamine, 6.77 g (0.04 mol) 4-phenylaniline, 0.115 g (0.0002 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.8 g (0.0004 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 3.84 g (0.04 mol) of sodium tert-butoxide, heating to 60 ℃ for reaction for 6 hours, cooling, adding water solution, washing an organic layer to be neutral, separating by silica gel column chromatography, eluting by petroleum ether to obtain 1.1 g of the compound shown as P-170-1, and obtaining 15.13% of yield.
Mass spectrometry detection is carried out on the compound shown in the P-170-1, and the molecular m/z is determined as follows: 726.
the nuclear magnetic detection is carried out on the compound shown in the P-170-1, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.75(m，4H)，δ7.59～7.41(m，14H)，δ7.38(m，8H)，δ7.15(s，8H)，δ5.65(s，2H)，δ3.59～3.50(m，4H)，δ1.15(t，6H)。
(3) Synthesis of P-170
500 ml three-port flask, nitrogen protection, 200 ml dry toluene, 7.27 g (0.01 mol) of the compound represented by P-170-1, 5.39 g (0.022 mol) of the compound represented by P-170-2, 0.0575 g (0.0001 mol) of Pd (dba) were added 2 (bis (dibenzylideneacetone palladium)), 0.4 g (0.0002 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 2.3 g (0.024 mol) of sodium tert-butoxide, heating to reflux reaction for 8 hours, cooling, adding water, concentrating the organic layer to dryness, separating by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 (volume ratio) to give 6.7 g of the compound represented by P-170 in 63.5% yield.
Mass spectrometry detection was carried out on the compound shown as P-170, and the molecular m/z is determined as follows: 1054.
the nuclear magnetic resonance detection was performed on the compound shown by P-170, and the data were analyzed as follows:
1 HNMR(500MHz，CDCl 3 ):δ7.73(m，4H)，δ7.55～7.38(m，14H)，δ7.33(m，8H)，δ7.29(m，4H)，δ7.18(m，4H)，δ7.10(s，8H)，δ4.65(s，4H)，δ3.62～3.49(m，12H)，δ3.40(s，6H)，δ1.15(t，6H)。
synthesis of examples 16 to P to 176
(1) Synthesis of N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine
Into a 500 ml three-necked flask, 19.5 g (0.1 mol) of N- (2- (2-methoxyethoxy) ethyl) aniline, 300 ml of toluene, 25 g (0.1 mol) of copper sulfate pentahydrate, stirring and heating to 80 ℃ for reaction for 48 hours, cooling, adding water, washing an organic layer to be neutral, separating by silica gel column chromatography, and petroleum ether: ethyl acetate = 8:2 to give 5.8g of N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine as a product in 29.9%.
Mass spectrum detection is carried out on the obtained product N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine, and the molecular m/z is determined as follows: 388.
the nuclear magnetism of the obtained product N4, N4' -bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl ] -4,4' -diamine is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.50(m，4H)，δ6.52(m，4H)，δ3.80(s，2H)，δ3.66(m，4H)，δ3.57～3.50(m，8H)，δ3.48～3.43(m，4H)，δ3.41(s，6H)。
(2) Synthesis of P-176
500 ml three-necked flask, nitrogen protection, 150 ml of dry toluene, 3.9 g (0.01 mol) of N4, N4 '-bis (2- (2 methoxyethoxy) ethyl) - [1,1' -biphenyl were added]-4,4' -diamine, 9.7 g (0.022 mol) of the compound represented by P-176-1, 0.0575 g (0.0001 mol) of Pd (dba) 2 (bis (dibenzylideneacetone palladium)) 0.4 g (0.0002 mol) toluene solution containing 10% tri-tert-butylphosphine, 2.3 g (0.024 mol) sodium tert-butoxide, heating to reflux reaction for 12 hours, cooling, and adding waterConcentrating the liquid and organic layer to dryness, separating by silica gel column chromatography, petroleum ether: ethyl acetate=9: 1 (volume ratio) to give 6.8 g of the compound represented by P-176 in a yield of 61.4%.
Mass spectrometry detection was carried out on the compound shown by P-176, and the molecular m/z is determined as follows: 1106.
the compound shown in P-176 is subjected to nuclear magnetic resonance detection, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.88(m，2H)，δ7.85(d，2H)，δ7.56～7.46(m，8H)，δ7.37～7.28(m，6H)，δ7.25～7.17(m，8H)，δ7.12(s，8H)，δ7.07(m，4H)，δ6.98(m，2H)，δ3.65(m，4H)，δ3.55～3.49(m，8H)，δ3.48～3.41(m，4H)，δ3.39(s，6H)，δ1.69(s，12H)。
synthesis of examples 17 to P to 180
(1) Synthesis of P-180-1
In a 250 ml autoclave, 5.53 g (0.01 mol) of 2,2', 7-tribromo-9, 9' -spirobifluorene, 4.5 g (0.1 mol) of ethylamine, 30 ml of toluene, 60 ml of N, N-dimethylformamide, 0.1 g of cuprous iodide, 5.52 g (0.04 mol) of potassium carbonate and after nitrogen substitution, the reaction was carried out for 8 hours under sealed heating to 100 ℃, the temperature was lowered, the aqueous solution was added, the organic layer was washed with water to neutrality and concentrated to dryness, and the silica gel column chromatography was separated, petroleum ether: ethyl acetate=9: 1 to obtain 3.1 g of the product shown as P-180-1 with the yield of 69.6%.
Mass spectrum detection is carried out on the obtained product shown by P-180-1, and the molecular m/z is determined as follows: 445.
the nuclear magnetism of the obtained product shown as P-180-1 is detected, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ7.87(m，1H)，δ7.82～7.77(m，3H)，δ7.47(m，1H)，δ7.28～7.21(m，2H)，δ6.90(d，2H)，δ6.87(d，1H)，δ6.72～6.64(m，3H)，δ3.56(s，3H)，δ3.45(m，6H)，δ1.28(t，9H)。
(2) Synthesis of P-180
500 ml three-port flask, nitrogen protection, adding 200 ml dry toluene, 4.46 g (0.01 mol) P-180-1 compound, 12.96 g (0.04 mol) P-180-2 4-bromo-N, N-diphenylaniline, 0.115 g (0.0002 mol) Pd (dba) 2 (bis (dibenzylideneacetone palladium)), 0.8 g (0.0004 mol) of toluene solution containing 10% of tri-tert-butylphosphine, 3.46 g (0.036 mol) of sodium tert-butoxide, heating and refluxing for reaction for 8 hours, cooling, adding water solution, washing an organic layer to be neutral, separating by silica gel column chromatography, and petroleum ether: ethyl acetate: dichloromethane = 9:0.5:0.5 (volume ratio) elution gave 9.2 g of the compound represented by P-180 in 78.3% yield.
Mass spectrum detection is carried out on the compound shown by P-180, and the molecular m/z is determined as follows: 1174.
the nuclear magnetic detection is carried out on the compound shown by P-180, and the data are analyzed as follows:
1 HNMR(500MHz，CDCl 3 )：δ8.13(d，1H)，δ7.95～7.82(m，5H)，δ7.67(m，1H)，δ7.29～7.20(m，14H)，δ7.15(s，12H)，δ7.09(m，12H)，δ7.02(m，6H)，δ6.66(d，2H)，δ6.21(m，2H)，δ3.43(m，3H)，δ3.34(m，3H)，δ1.15(t，9H)。
the following examples and comparative examples provide organic electroluminescent devices using the following specific structures of materials:
examples 1-1 to 1-18, comparative examples 1-1 and 1-2
The above numbered examples selected the compounds of the present invention as hole transport materials in organic electroluminescent devices, and comparative examples 1-1 and 1-2 respectively selected NPB and HT-2 as hole transport materials in organic electroluminescent devices, as detailed in table 1.
The organic electroluminescent device structure is as follows: ITO/HIL02 (100 nm)/hole transport material (40 nm)/EM 1 (30 nm)/TPBI (30 nm)/LiF (0.5 nm)/Al (150 nm).
The preparation process of the organic electroluminescent device comprises the following steps:
carrying out ultrasonic treatment on a glass substrate coated with an ITO transparent conductive layer (serving as an anode) in a cleaning agent, then flushing in deionized water, then carrying out ultrasonic degreasing in a mixed solvent of acetone and ethanol, then baking in a clean environment until complete dewatering, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam to improve the property of the surface and the bonding capability with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporation HIL02 is used as a hole injection layer on the anode, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 100nm;
vacuum evaporating the compound or the contrast material serving as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 40nm;
vacuum evaporating EM1 on the hole transport layer to obtain an organic light-emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
vacuum evaporating TPBI on the organic light-emitting layer to serve as an electron transport layer of the organic electroluminescent device; the vapor deposition rate is 0.1nm/s, and the total film thickness of vapor deposition is 30nm;
LiF of 0.5nm and Al of 150nm are vacuum evaporated on the electron transport layer as an electron injection layer and a cathode.
Performance testing
The organic electroluminescent devices prepared in the above examples and comparative examples were tested for brightness, driving voltage, and current efficiency using an OLED-1000 multi-channel accelerated aging life and photochromic performance analysis system manufactured by Hangzhou remote, and the test results are shown in table 1.
TABLE 1
| Hole transport material | The required brightness cd/m 2 | Drive voltage V | Current efficiency cd/a | |
| Comparative examples 1 to 1 | NPB | 1000 | 6.15 | 1.63 |
| Comparative examples 1 to 2 | HT-2 | 1000 | 5.22 | 1.73 |
| Example 1-1 | P-18 | 1000 | 4.69 | 1.68 |
| Examples 1 to 2 | P-11 | 1000 | 4.94 | 1.83 |
| Examples 1 to 3 | P-14 | 1000 | 5.08 | 1.71 |
| Examples 1 to 4 | P-32 | 1000 | 4.26 | 1.88 |
| Examples 1 to 5 | P-38 | 1000 | 5.13 | 1.84 |
| Examples 1 to 6 | P-47 | 1000 | 4.5 | 1.71 |
| Examples 1 to 7 | P-98 | 1000 | 4.71 | 1.79 |
| Examples 1 to 8 | P-107 | 1000 | 5.13 | 1.77 |
| Examples 1 to 9 | P-113 | 1000 | 4.66 | 1.73 |
| Examples 1 to 10 | P-122 | 1000 | 5.17 | 1.66 |
| Examples 1 to 11 | P-131 | 1000 | 4.74 | 1.88 |
| Examples 1 to 12 | P-140 | 1000 | 4.51 | 1.73 |
| Examples 1 to 13 | P-145 | 1000 | 4.71 | 1.89 |
| Examples 1 to 14 | P-149 | 1000 | 4.50 | 1.78 |
| Examples 1 to 15 | P-158 | 1000 | 4.32 | 2.05 |
| Examples 1 to 16 | P-161 | 1000 | 4.49 | 1.82 |
| Examples 1 to 17 | P-162 | 1000 | 4.45 | 1.76 |
| Examples 1 to 18 | P-170 | 1000 | 4.36 | 1.89 |
As can be seen from the above table, compared with the conventional NPB and HT-2, the compound provided by the invention can be used as a hole transport material of an organic electroluminescent device, so that the luminous efficiency and the comprehensive performance of the driving voltage of the device can be improved.
Examples 2-1 to 2-17, comparative example 2-1
The above numbered examples selected the compounds of the present invention as hole injection materials in organic electroluminescent devices, and comparative example 2-1 selected HIL02 as hole injection materials in organic electroluminescent devices, as detailed in table 2.
The organic electroluminescent device structure is as follows: ITO/hole injection material (100 nm)/NPB (40 nm)/EM 1 (30 nm)/TPBI (30 nm)/LiF (0.5 nm)/Al (150 nm).
The preparation process of the organic electroluminescent device comprises the following steps:
carrying out ultrasonic treatment on a glass substrate coated with an ITO transparent conductive layer (serving as an anode) in a cleaning agent, then flushing in deionized water, then carrying out ultrasonic degreasing in a mixed solvent of acetone and ethanol, then baking in a clean environment until complete dewatering, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam to improve the property of the surface and the bonding capability with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, evaporating a contrast material HIL02 or the compound of the invention on the anode to serve as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 100nm;
vacuum evaporation of NPB as hole transport layer on the hole injection layer, with evaporation rate of 0.1nm/s and thickness of 40nm;
vacuum evaporating EM1 on the hole transport layer to obtain an organic light-emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
vacuum evaporating TPBI on the organic light-emitting layer to serve as an electron transport layer of the organic electroluminescent device; the vapor deposition rate is 0.1nm/s, and the total film thickness of vapor deposition is 30nm;
LiF of 0.5nm and Al of 150nm are vacuum evaporated on the electron transport layer as an electron injection layer and a cathode.
Performance testing
The organic electroluminescent devices prepared in the above examples and comparative examples were tested for brightness, driving voltage, and current efficiency using an OLED-1000 multi-channel accelerated aging life and photochromic performance analysis system manufactured by Hangzhou remote, and the test results are shown in table 2.
TABLE 2
| Hole injection material | The required brightness cd/m 2 | Drive voltage V | Current efficiency cd/a | |
| Comparative example 2-1 | HIL02 | 1000 | 6.13 | 1.64 |
| Example 2-1 | P-3 | 1000 | 5.49 | 1.71 |
| Examples 2 to 3 | P-29 | 1000 | 4.65 | 1.8 |
| Examples 2 to 4 | P-59 | 1000 | 4.96 | 1.7 |
| Examples 2 to 5 | P-76 | 1000 | 4.85 | 1.66 |
| Examples 2 to 6 | P-78 | 1000 | 5.21 | 1.76 |
| Examples 2 to 7 | P-85 | 1000 | 5.13 | 1.78 |
| Examples 2 to 8 | P-91 | 1000 | 4.58 | 1.82 |
| Examples 2 to 9 | P-107 | 1000 | 5.09 | 1.76 |
| Examples 2 to 10 | P-115 | 1000 | 4.83 | 1.83 |
| Examples 2 to 11 | P-121 | 1000 | 4.89 | 1.66 |
| Examples 2 to 12 | P-129 | 1000 | 5.14 | 1.89 |
| Examples 2 to 13 | P-148 | 1000 | 4.84 | 1.65 |
| Examples 2 to 14 | P-152 | 1000 | 4.72 | 1.72 |
| Examples 2 to 15 | P-158 | 1000 | 6.06 | 1.72 |
| Examples 2 to 16 | P-176 | 1000 | 5.76 | 1.88 |
| Examples 2 to 17 | P-180 | 1000 | 5.41 | 1.97 |
As shown in the above table, compared with the traditional HIL02, the compound provided by the invention can be used as a hole injection material of an organic electroluminescent device, and can improve the luminous efficiency and reduce the driving voltage.
Examples 3-1 to 3-6, comparative examples 3-1 and 3-2
The above numbered examples select the compound of the present invention as a hole transport material in an organic electroluminescent device, the comparative examples 3-1 and 3-2 select NPB and HT-2 as hole transport materials in an organic electroluminescent device, respectively, and in the above examples and comparative examples, the hole transport layer was prepared by a solution method.
The organic electroluminescent device structure is as follows: ITO/HIL02 (100 nm)/hole transport material/EM 1 (30 nm)/TPBI (30 nm)/LiF (0.5 nm)/Al (150 nm).
The preparation process of the organic electroluminescent device comprises the following steps:
carrying out ultrasonic treatment on a glass substrate coated with an ITO transparent conductive layer (serving as an anode) in a cleaning agent, then flushing in deionized water, then carrying out ultrasonic degreasing in a mixed solvent of acetone and ethanol, then baking in a clean environment until complete dewatering, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam to improve the property of the surface and the bonding capability with a hole injection layer;
placing the glass substrate in a vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporation HIL02 is used as a hole injection layer on the anode, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 100nm;
the above glass substrate on which the hole injection layer had been evaporated was transferred into a glove box filled with nitrogen gas, and a chlorobenzene solution of the compound of the present invention or a comparative compound was spin-coated on the hole injection layer at 0.02% (by weight), the spin-coating rotation speed was 1000 rpm, the time was 60 seconds, and then the above glass substrate was heated at 80 ℃ for 2 hours, the solvent was removed in vacuo, and the film thickness of the spin-coated hole transport layer was measured by a step sizer (model amitio XP-2surface profiler) and is shown in table 3.
Transferring the glass substrate which is spin-coated with the hole transport layer in the previous step into a vacuum chamber, and vacuum evaporating EM1 serving as an organic light-emitting layer of the device on the hole transport layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 30nm;
vacuum evaporating TPBI on the organic light-emitting layer to serve as an electron transport layer of the organic electroluminescent device; the vapor deposition rate is 0.1nm/s, and the total film thickness of vapor deposition is 30nm;
LiF of 0.5nm and Al of 150nm are vacuum evaporated on the electron transport layer as an electron injection layer and a cathode.
Performance testing
The organic electroluminescent devices prepared in the above examples and comparative examples were tested for brightness, driving voltage, and current efficiency using an OLED-1000 multi-channel accelerated aging life and photochromic performance analysis system manufactured by Hangzhou remote, and the test results are shown in table 3.
TABLE 3 Table 3
As can be seen from the above table, when the hole transport layer is prepared by a solution method, compared with the conventional NPB and HT-2, the compound provided by the invention can be used as a hole transport material of an organic electroluminescent device, and can improve the luminous efficiency and reduce the driving voltage.
Examples 4-1 to 4-8, comparative example 4-1
The above numbered examples selected the compound of the present invention as a hole injection material in an organic electroluminescent device, comparative example 4-1 selected HIL02 as a hole injection material in an organic electroluminescent device, and in the above examples and comparative examples, the hole injection layer was prepared using a solution method.
The organic electroluminescent device structure is as follows: ITO/hole injection material/NPB (40 nm)/EM 1 (30 nm)/TPBI (30 nm)/LiF (0.5 nm)/Al (150 nm).
The preparation process of the organic electroluminescent device comprises the following steps:
carrying out ultrasonic treatment on a glass substrate coated with an ITO transparent conductive layer (serving as an anode) in a cleaning agent, then flushing in deionized water, then carrying out ultrasonic degreasing in a mixed solvent of acetone and ethanol, then baking in a clean environment until complete dewatering, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam to improve the property of the surface and the bonding capability with a hole injection layer;
the above glass substrate was transferred into a glove box filled with nitrogen gas, a chlorobenzene solution of the compound of the present invention or the comparative compound was spin-coated on the hole injection layer at a spin-coating speed of 1000 rpm for 60 seconds, and then the above glass substrate was heated at 80 ℃ for 2 hours, the solvent was removed in vacuo, and the film thickness of the spin-coated hole injection layer was measured by a step sizer (model amitio XP-2surface profiler) and is shown in table 4.
Placing the above glass substrate with spin-coated hole injection layer into a vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporation of NPB as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 40nm;
vacuum evaporating EM1 on the hole transport layer to obtain an organic light-emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
vacuum evaporating TPBI on the organic light-emitting layer to serve as an electron transport layer of the organic electroluminescent device; the vapor deposition rate is 0.1nm/s, and the total film thickness of vapor deposition is 30nm;
LiF of 0.5nm and Al of 150nm are vacuum evaporated on the electron transport layer as an electron injection layer and a cathode.
Performance testing
The organic electroluminescent devices prepared in the above examples and comparative examples were tested for brightness, driving voltage, and current efficiency using an OLED-1000 multi-channel accelerated aging life and photochromic performance analysis system manufactured by Hangzhou remote, and the test results are shown in table 4.
TABLE 4 Table 4
As can be seen from the above table, when the hole injection layer is prepared by a solution method, compared with the conventional HIL02, the compound provided by the present invention can be used as a hole injection material of an organic electroluminescent device, so as to improve the light emitting efficiency and reduce the driving voltage.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (9)
1. A compound, characterized in that the compound has a structure represented by formula III;
in formula III, the Ar 1 Any one selected from biphenylene, 9-dimethyl-substituted fluorenylene, phenylene and naphthylene;
in formula III, the Ar 2 、Ar 3 Each independently selected from a group represented by formula II or any one of phenyl, naphthyl, 9-dimethyl-substituted fluorenyl, biphenyl, and Ar 2 And Ar is a group 3 At least one of which is selected from the group represented by formula II;
in formula II, the wavy line represents the bond of the group;
in the formula II, W is selected from any one of phenylene, biphenylene, naphthylene, 9-dimethyl substituted fluorenylene and terphenylene;
in formula II, the Ar 5 And Ar is a group 6 Each independently selected from phenyl, naphthyl, 9-dimethyl-substituted fluorenyl, biphenyl,Any one of terphenyl and triphenylyl;
in the formula III, the X, Y is independently selected from any one of ethyl, propyl, butyl and cyclohexyl;
any hydrogen atom in formula III is replaced with deuterium or not replaced with deuterium;
the compounds do not include the following:
2. the compound of claim 1, wherein the compound has any one of the following compounds:
3. use of a compound according to claim 1 or 2, characterized in that the compound is applied in an organic electroluminescent device.
4. Use according to claim 3, characterized in that the compound according to claim 1 or 2 is used as hole transport layer material or hole injection layer material for an organic electroluminescent device.
5. An organic electroluminescent device comprising an anode layer and a cathode layer, and an organic layer disposed between the anode layer and the cathode layer, wherein the organic layer comprises the compound of claim 1 or 2.
6. The organic electroluminescent device according to claim 5, wherein the organic layer comprises a hole injection layer containing the compound according to claim 1 or 2.
7. The organic electroluminescent device according to claim 5, wherein the organic layer comprises a hole transport layer containing the compound according to claim 1 or 2.
8. A display panel, characterized in that the display panel comprises the organic electroluminescent device according to any one of claims 5 to 7.
9. A display device comprising the organic electroluminescent device according to any one of claims 5 to 7 or the display panel according to claim 8.
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| KR100577179B1 (en) * | 2001-10-30 | 2006-05-10 | 엘지전자 주식회사 | Organic Electroluminescent Element |
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