CN113292481A - 有机电致发光化合物、其制备方法和应用 - Google Patents
有机电致发光化合物、其制备方法和应用 Download PDFInfo
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- CN113292481A CN113292481A CN202110352984.XA CN202110352984A CN113292481A CN 113292481 A CN113292481 A CN 113292481A CN 202110352984 A CN202110352984 A CN 202110352984A CN 113292481 A CN113292481 A CN 113292481A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000000376 reactant Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- -1 dimethyl fluorenyl Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 7
- 125000002950 monocyclic group Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 125000003003 spiro group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 239000004305 biphenyl Chemical group 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002346 layers by function Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 43
- 230000005525 hole transport Effects 0.000 abstract description 40
- 230000009477 glass transition Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000021615 conjugation Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000543 intermediate Substances 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000005909 Kieselgur Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 235000019341 magnesium sulphate Nutrition 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 125000005264 aryl amine group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000011521 glass Substances 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
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- 238000002386 leaching Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000005266 diarylamine group Chemical group 0.000 description 2
- 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 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-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)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- MFMVRILBADIIJO-UHFFFAOYSA-N benzo[e][1]benzofuran Chemical compound C1=CC=C2C(C=CO3)=C3C=CC2=C1 MFMVRILBADIIJO-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- GIFAOSNIDJTPNL-UHFFFAOYSA-N n-phenyl-n-(2-phenylphenyl)naphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1C1=CC=CC=C1 GIFAOSNIDJTPNL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C211/54—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 two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- 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
- C07C211/58—Naphthylamines; N-substituted derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
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Abstract
本发明公开了有机电致发光化合物、其制备方法和应用,涉及发光材料技术领域。本发明提出的有机电致发光化合物中π共轭效应使得其有很强的空穴传输能力、较高的玻璃化转变温度(Tg)温度。该有机电致发光化合物作为OLED发光器件的空穴传输材料或者其他有机化合物层时,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率,有利于延长使用寿命。
Description
技术领域
本发明涉及发光材料技术领域,具体而言,涉及有机电致发光化合物、其制备方法和应用。
背景技术
近些年OLED技术已经取得了巨大的研究进展,在发光效率方面,OLED远远高于PDP、CRT的水平。OLED发光器件犹如三明治的结构,由空穴注入层、空穴传输层、发光层、电子传输层和电子注入层等结构组成。空穴传输层(HTL)负责调节空穴的注入速度和注入量,空穴传输材料直接影响OLED的效率和寿命。
现有空穴传输区域中常用的化合物包括酞菁铜(CuPc)、4,4’-双[N-(1-萘基)-N-苯基氨基]联苯(NPB)、N,N’-二苯基-N,N’-双(3-甲基苯基)-(1,1’-联苯基)-4,4’-二胺(TPD)、4,4’,4”-三(3-甲基苯基苯基氨基)三苯胺(MTDATA)等。
然而,使用这些材料作为空穴传输层的OLED在量子效率和使用寿命方面均存在问题。这是因为:空穴传输材料通常具有低的最高已占据分子轨道(HOMO)值,在发光层中生成的激子扩散到空穴传输层界面或者空穴传输层侧,最终导致在发光层内界面的发光或者发光层内的电荷不均衡,从而在空穴传输层的界面上发光,使有机电致发光器件的色纯度及效率变低。目前公开的有机电致发光化合物,其发光效率和寿命均有一定不足。因此,开发一种发光效率高、使用寿命长、具有低驱动电压的材料是目前需要解决的技术问题。
鉴于此,特提出本发明。
发明内容
本发明的目的在于提供一种有机电致发光化合物及其制备方法,旨在提升化合物的空穴传输能力,提高化合物的玻璃化转变温度。
本发明的另一目的在于提供一种空穴传输层和OLED发光器件,将上述化合物作为OLED发光器件的空穴传输材料时,能够降低器件的起始电压,提高有机电致发光器件的效率。
本发明是这样实现的:
本发明提出一种有机电致发光化合物,其结构式为:
其中,a和b各自独立地表示0、1、2、3或4;c表示0、1、2或3;
X和Y各自独立地表示化学键、O、S、C(R4R5)、Si(R6R7)和NR8中的任意一种;
Ar1-Ar4和L1-L4各自独立地表示取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C10-C30)稠环基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6-C60)芳基胺基、取代或未取代的(C10-C30)螺环基,或与相邻取代基连接成单环或(C3-C30)脂肪族环或(C6-C30)芳香族环;
R1-R3各自独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C3-C30)环烷基、取代或未取代的(C3-C30)杂环烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6~C60)芳基胺基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C60)芳氧基,或与相邻取代基连接形成单环或(C3-C30)多环脂肪族环或(C3-C30)芳香族环。
本发明还提出一种有机电致发光化合物的制备方法,由反应物A-I和反应物B-I进行催化反应并分离得到中间体C-I,将中间体C-I与反应物D-I进行催化反应并分离得到中间体E-I,将中间体E-I和反应物F-I进行催化反应;
其合成路线如下:
本发明还提出一种有机化合物功能层,其由上述的有机电致发光化合物制备而得。
本发明还提出一种OLED发光器件,包括第一电极、第二电极和位于第一电极和第二电极之间的一个或多个有机化合物层,至少一个有机化合物层由上述有机电致发光化合物制备而得。
本发明具有以下有益效果:本发明提出的有机电致发光化合物中π共轭效应使得其有很强的空穴传输能力,通过引入双芳胺侧链使化合物整体的空间结构呈放射状,使得分子间的距离变大,有利于减小分子间的凝聚力,减少结晶可能性,使得本发明申请化合物具有较高的玻璃化转变温度(Tg)温度。
该有机电致发光化合物作为OLED发光器件的空穴传输材料或者其他有机化合物层时,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率,有利于延长使用寿命。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
在本发明实施例的技术方案中,术语“经取代或未经取代的”意指被选自以下的一个、两个或更多个取代基取代:氘;卤素基团;腈基;羟基;羰基;酯基;甲硅烷基;硼基;经取代或未经取代的烷基;经取代或未经取代的环烷基;经取代或未经取代的烷氧基;经取代或未经取代的烯基;经取代或未经取代的烷基胺基;经取代或未经取代的杂环基胺基;经取代或未经取代的芳基胺基;经取代或未经取代的芳基;和经取代或未经取代的杂环基,或者被以上所示的取代基中的两个或更多个取代基相连接的取代基取代,或者不具有取代基。例如,“两个或更多个取代基相连接的取代基”可以包括联苯基。换言之,联苯基可以为芳基,或者可以解释为两个苯基相连接的取代基。
本发明实施例提供了一种有机电致发光化合物,其结构式为:
需要说明的是,本发明实施例的化合物含有芳胺基给电子基团,具有优异的空穴传输性能,且具有高的三线态能级(T1),作为OLED发光器件的电子阻挡层材料使用可有效阻挡发光层的激子能量传递至空穴传输层中,提高激子在发光层中的复合效率,提高能量利用率,从而提高器件的发光效率。
此外,本发明实施例提供的化合物通过引入的双芳胺侧链,使化合物整体的空间结构呈放射状,使得分子间的距离变大,有利于减小分子间的凝聚力,减少结晶可能性,使得本发明实施例中的化合物具有较高的玻璃化转变温度(Tg)温度。
通式中,a和b各自独立地表示0、1、2、3或4;c表示0、1、2或3。a、b和c的取值可以相同也可以不同,如a取0时,b可以取0、1、2、3或4,c可以取0、1、2或3;同样,a取1、2、3或4时,b也可以取0、1、2、3或4,c也可以取0、1、2或3。
可选地,a、b和c各自独立地表示0或1,如a取0时,b可以取0或1,c可以取0或1;同样,a取1时,b也可以取0或1,c也可以取0或1。
通式中,X和Y各自独立地表示化学键、O、S、C(R4R5)、Si(R6R7)和NR8中的任意一种。一般,当X为化学键时,Y不为O;当Y为化学键时,X不为O。X和Y可以相同也可以不同,在此不做一一列举。
可选地,X和Y与两侧的苯环形成的结构各自独立地选自以下基团中的任意一种:
其中,R1-R8各自独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C3-C30)环烷基、取代或未取代的(C3-C30)杂环烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6~C60)芳基胺基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C60)芳氧基,或与相邻取代基连接形成单环或(C3-C30)多环脂肪族环或(C3-C30)芳香族环。R1-R8所表示的取代基可以相同也可以不同,分别独立地选自上述取代基或者成环。
在一些实施例中,R1-R8中至少一个碳原子被置换为杂原子,杂原子选自氮、氧和硫中的任意一种。
可选地,R1-R8各自独立地选自甲基、乙基、丙基、叔丁基、烷氧基、烷巯基、芳氧基、苯基、联苯基、萘基、二甲基芴基,二苯基芴基和螺环基中的任意一种。通过进一步控制R1-R8中的取代基类型,有利于进一步提升化合物的空穴传输性能。
通式中,Ar1-Ar4和L1-L4各自独立地表示取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C10-C30)稠环基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6-C60)芳基胺基、取代或未取代的(C10-C30)螺环基,或与相邻取代基连接成单环或(C3-C30)脂肪族环或(C6-C30)芳香族环;在一些实施例中,Ar1-Ar4和L1-L4中至少一个碳原子被置换为杂原子,杂原子选自氮、氧和硫中的任意一种。Ar1-Ar4和L1-L4共8个基团,可以相同也可以不同,各自独立地从上述取代基中进行选择或者与相邻取代基成环。
可选地,Ar1-Ar4和L1-L4各自独立地选自萘基、蒽基、菲基、苯并菲,苯基、咔唑基、叔丁基苯基、甲基苯基、三联苯基、联苯基、二苯并呋喃基、二苯并噻吩基、芴基和螺基及其衍生物中的任意一种。通过进一步控制Ar1-Ar4和L1-L4中的取代基类型,有利于进一步提升化合物的空穴传输性能,作为OLED发光器件的空穴传输材料时,有利于进一步降低器件的起始电压,提高有机电致发光器件的效率,并延长使用寿命。
为进一步保证化合物的空穴传输性能,发明人对化合物的具体结构进行了列举,有机电致发光化合物可以选自以下化合物中的任意一种:
需要说明的是,以上87种化合物均具备很强的空穴传输能力,分子间的距离更大,具有更高的玻璃化转变温度(Tg)温度。使用上述87种化合物作为空穴传输层材料制备的有机电致发光器件可以表现出高的发光效率及长寿命并降低驱动电压。
本发明实施例还提出了一种有机电致发光化合物的制备方法,用于制备通式中的化合物,包括:由反应物A-I和反应物B-I进行催化反应并分离得到中间体C-I,将中间体C-I与反应物D-I进行催化反应并分离得到中间体E-I,将中间体E-I和反应物F-I进行催化反应;
其合成路线如下:
以上原料和中间体中取代基的类型参照关于化合物的介绍,在此不做重复赘述。
通过3步催化反应制备得到符合通式要求的产品,每步催化反应均控制反应温度为100-120℃,反应时间为8-12h。反应温度可以为100℃、110℃、120℃,也可以为相邻温度取值中的任意值。反应时间可以为8h、9h、10h、11h、12h,也可以为相邻时间取值中的任意值。
具体地,三步催化反应中所采用的溶剂不限,可以为甲苯、乙醇、水、丙酮等,可以为混合溶剂,在此不做限定。
在一些实施例中,反应物A-I和反应物B-I进行催化反应所采用的催化剂包括Pd2(dba)3、P(t-Bu)3和t-BuONa;中间体C-I与反应物D-I进行催化反应所采用的催化剂包括Pd2(dba)3、P(t-Bu)3和t-BuONa;中间体E-I和反应物F-I进行催化反应所采用的催化剂包括四(三苯基膦)钯和碳酸钾。通过进一步控制三步催化反应中的催化剂选择,可以进一步提升反应效率。
可选地,每步催化反应均是在保护气体氛围下进行反应。保护气体可以为氮气等,也可以为其他惰性气体,在此不做限定。
进一步地,分离得到中间体C-I和中间体E-I的过程包括:将反应后的混合物进行过滤,将滤液和水混合分离有机相和水相,对水相进行萃取得到有机相,合并有机相进行洗脱纯化。通过进一步优化分离的步骤,以提升分离的效率,并保证中间体可以更充分地分离出来。
在一些实施例中,在进行洗脱纯化之前,对合并后的有机相进行干燥以去除溶剂。
在一些实施例中,为了提升洗脱纯化的效果,洗脱纯化是采用二氯甲烷和石油醚的混合液作为洗脱剂,采用管柱色谱法进行纯化,二氯甲烷和石油醚的体积比为1:1-9。通过控制洗脱剂的选择和用量,以便提高分离后中间体的纯度,保证最终产品的纯度和收率。
进一步地,在中间体E-I和反应物F-I进行催化反应之后进行冷却、过滤,对过滤得到的固体物料进行洗涤并干燥,再进行重结晶。通过冷却使固体充分析出,经过过滤配合水洗和醇洗可以去除盐类,再经过重结晶分离得到最终产品。
下面对本发明实施例的制备方法做更具体举例介绍。
合成路线如下:
具体如下:
(1)在反应容器中加入化学式反应物A-I(1.0eq)和反应物B-I(1.1eq)溶于500mL甲苯之后,在氮气氛围下加入Pd2(dba)3(0.01eq)、P(t-Bu)3(0.055eq)、t-BuONa(2.2eq)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体C-I。
(2)在反应容器中加入中间体C-I(1.0eq)和反应物D-I(0.8eq)溶于300mL甲苯之后,在氮气氛围下加入Pd2(dba)3(0.01eq)、P(t-Bu)3(0.05eq)、t-BuONa(2.0eq)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体E-I。
(3)N2保护下,将中间体E-I(1.0eq)、反应物F-I(1.1eq)、四(三苯基膦)钯(0.01eq)和碳酸钾(2.2eq)分别加入到甲苯、乙醇、水的混合溶剂中,升温至100-120℃回流反应8h,反应结束后,冷却至室温,待固体析出完毕后,抽滤后用水洗涤除去盐,再用少量乙醇淋洗,干燥滤饼。置于1,4-二氧六环中重结晶,得到通式I所示化合物。
本发明实施例还提出一种有机化合物功能层,其由上述有机电致发光化合物制备而得。该功能层可以为空穴传输层,其由上述有机电致发光化合物制备而得。该空穴传输层由于原料选自本发明实施例所提供的化合物,具备非常优异的空穴传输能力。
本发明实施例还提出一种OLED发光器件,包括第一电极、第二电极和位于第一电极和第二电极之间的一个或多个有机化合物层,至少一个有机化合物层由上述有机电致发光化合物制备而得。由于有机化合物层具有很高的空穴传输速率,能够降低器件的起始电压,提高有机电致发光器件的效率,有利于延长使用寿命。
需要说明的是,OLED发光器件的具体结构可以参照现有的器件结构,在此不做具体限定。
在一些实施例中,第一电极和第二电极之间设置包括空穴注入层、空穴传输层、发光辅助层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层的至少一层或多层。
具体地,第一电极作为阳极,阳极优选包含具有高逸出功的材料。例如阳极材料可以为Ag、Pt或Au,优选的阳极材料是导电混合金属氧化物,特别优选的是氧化锡铟(ITO)或氧化铟锌(IZO)。
在一些实施例中,空穴传输层包括通式I所示的含有萘并呋喃的有机电致发光化合物,其他各层的原料可以不做限定。
在一些实施例中,电子阻挡层可以设置在空穴传输层与发光层之间,也可以设置在发光辅助层和发光层之间。作为电子阻挡层,可以使用本领域中已知的材料,例如基于芳基胺的有机材料。
发光层的材料是一种通过分别接收来自空穴传输层和电子传输层的空穴和电子,并将所接收的空穴和电子结合而能发出可见光的材料。此外,发光层可以包含主体材料和掺杂材料;主体材料和掺杂材料的质量比为90-99.5:0.5-10;掺杂材料可以包括荧光掺杂和磷光掺杂。
具体地,发光层可以发射红色、绿色或蓝色的光,并且可以由磷光材料或荧光材料形成。发光材料是能够通过接收分别来自空穴传输层和电子传输层的空穴和电子并使空穴与电子结合而发出在可见光区域内的光的材料。磷光掺杂材料的包括铱、铂等的金属络合物的磷光材料。例如,可以使用Ir(ppy)3等绿色磷光材料,FIrpic、FIr6等蓝色磷光材料和Btp2Ir(acac)等红色磷光材料。对于荧光掺杂材料,可以用现有技术中公知的具有电子传输作用的化合物。
空穴阻挡层材料,可以使用现有技术中公知的具有空穴阻挡作用的化合物,例如,浴铜灵(BCP)等菲咯啉衍生物、噁唑衍生物、三唑衍生物、三嗪衍生物等,但不限于此。
电子注入层可以起到促进电子注入的作用,有传输电子的能力,防止发光层中产生的激子迁移至空穴注入层。
第二电极作为阴极,优选包含具有低逸出功的金属。该层的层厚度优选在0.5和5nm之间。
本发明的器件可以用于有机发光器件、有机太阳电池、电子纸、有机感光体或有机薄膜晶体管。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
以下是本发明的实施举例,下面实施例是为了帮助本发明理解而提供的,并不是将本发明的内容限定在这个范围。并且本发明的各实施例中具体没有列举化合物的制备方法是有关行业通常应用的方法,实施例中记载的方法,在制备其他化合物时,也可以参考。
实施例1:化合物12的合成
本发明实施例提供的制备方法合成路线如下:
具体步骤如下:
(1)在反应容器中加入化学式反应物A-12(100mmol)和反应物B-12(110mmol)溶于500mL甲苯之后,在氮气氛围下加入Pd2(dba)3(1.0mmol)、P(t-Bu)3(5.5mmol)、t-BuONa(220mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体C-12(50.4g,Ms:622.39,产率:81%)。
(2)在反应容器中加入中间体C-12(75mmol)和反应物D-12(60mmol)溶于300mL甲苯之后,在氮气氛围下加入Pd2(dba)3(0.75mmol)、P(t-Bu)3(1.5mmol)、t-BuONa(150mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体E-12(36.0g,Ms:713.76,产率为84%)。
(3)N2保护下,将中间体E-12(45mmol)、反应物F-12(49.5mmol)、四(三苯基膦)钯(0.45mmol)和碳酸钾(99mmol)分别加入到300mL甲苯、100mL乙醇、100mL水的混合溶剂中,升温至100℃回流反应8h,反应结束后,冷却至室温,待固体析出完毕后,抽滤后用水洗涤除去盐,再用少量乙醇淋洗,干燥滤饼。置于1,4-二氧六环(300mL)中重结晶,得到化合物12(30.4g,77%)。
对所得化合物12进行检测分析,结果如下:
质谱测试:理论值为876.16;测试值为876.42。
元素分析:
理论值为:C,89.11;H,6.10;N,4.80;
测试值为:C,87.11;H,6.11;N,4.80。
实施例2:化合物34的合成
本发明实施例提供的制备方法合成路线如下:
具体步骤如下:
(1)在反应容器中加入化学式反应物A-34(100mmol)和反应物B-34(110mmol)溶于500mL甲苯之后,在氮气氛围下加入Pd2(dba)3(1.0mmol)、P(t-Bu)3(5.5mmol)、t-BuONa(220mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体C-34(46.6g,Ms:582.32,产率为80%)。
(2)在反应容器中加入中间体C-34(75mmol)和反应物D-34(60mmol)溶于300mL甲苯之后,在氮气氛围下加入Pd2(dba)3(0.75mmol)、P(t-Bu)3(1.5mmol)、t-BuONa(150mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体E-34(34.5g,Ms:755.84,产率为76%)。
(3)N2保护下,将中间体E-34(45mmol)、反应物F-34(49.5mmol)、四(三苯基膦)钯(0.45mmol)和碳酸钾(99mmol)分别加入到300mL甲苯、100mL乙醇、100mL水的混合溶剂中,升温至100℃回流反应8h,反应结束后,冷却至室温,待固体析出完毕后,抽滤后用水洗涤除去盐,再用少量乙醇淋洗,干燥滤饼。置于1,4-二氧六环(300mL)中重结晶,得到化合物34(31.7g,81%)。
对所得化合物34进行检测分析,结果如下:
质谱测试:理论值为869.21;测试值为869.37。
元素分析:
理论值为:C,57.75;H,4.33;Br,13.72;I,21.79;N,2.41;
测试值为:C,57.74;H,4.34;Br,13.73;I,21.79;N,2.40。
实施例3:化合物75的合成
本发明实施例提供的制备方法合成路线如下:
具体步骤如下:
(1)在反应容器中加入化学式反应物A-75(100mmol)和反应物B-75(110mmol)溶于500mL甲苯之后,在氮气氛围下加入Pd2(dba)3(1.0mmol)、P(t-Bu)3(5.5mmol)、t-BuONa(220mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体C-75(43.2g,Ms:561.05,产率为77%)。
(2)在反应容器中加入中间体C-75(75mmol)和反应物D-75(60mmol)溶于300mL甲苯之后,在氮气氛围下加入Pd2(dba)3(0.75mmol)、P(t-Bu)3(1.5mmol)、t-BuONa(150mmol)。添加后,使反应温度缓慢升温到110℃,并且搅拌混合物10h。使用硅藻土趁热抽滤,除去盐和催化剂,滤液冷却至室温后,接着将蒸馏水添加到滤液中进行洗涤,分液后保留有机相,用乙酸乙酯萃取水相取有机相,合并有机相再用硫酸镁进行干燥,使用旋转式蒸发器去除溶剂。以二氯甲烷:石油醚体积比为1:(1-9)作为洗脱剂,用管柱色谱法纯化剩余物质,获得中间体E-75(29.0g,Ms:603.65,产率为80%)。
(3)N2保护下,将中间体E-75(45mmol)、反应物F-75(49.5mmol)、四(三苯基膦)钯(0.45mmol)和碳酸钾(99mmol)分别加入到300mL甲苯、100mL乙醇、100mL水的混合溶剂中,升温至100℃回流反应8h,反应结束后,冷却至室温,待固体析出完毕后,抽滤后用水洗涤除去盐,再用少量乙醇淋洗,干燥滤饼。置于1,4-二氧六环(300mL)中重结晶,得到化合物75(29.8g,82%)。
对所得化合物75进行检测分析,结果如下:
质谱测试:理论值为808.13;测试值为808.44。
元素分析:
理论值为:C,87.69;H,7.11;N,5.20;
测试值为:C,87.68;H,7.12;N,5.21。
实施例4-实施例18
参照实施例1至3的合成方法完成对化合物3,10,19,23,28,40,45,51,56,60,65,68,72,78,85的合成,质谱和分子式列于下表1。
另外,需要说明,本申请其他化合物参照上述所列举的实施例的合成方法即可获得,所以在此不再一一列举。
表1合成化合物的参数说明
实施例 | 化合物 | 分子式 | 质谱理论值 | 质谱测试值 | 产率% |
实施例4 | 3 | C<sub>60</sub>H<sub>43</sub>N<sub>3</sub> | 806.03 | 806.45 | 80 |
实施例5 | 10 | C<sub>60</sub>H<sub>41</sub>N<sub>3</sub>O | 820.01 | 820.19 | 85 |
实施例6 | 19 | C<sub>57</sub>H<sub>44</sub>N<sub>2</sub> | 756.99 | 756.86 | 83 |
实施例7 | 23 | C<sub>63</sub>H<sub>52</sub>N<sub>2</sub> | 837.12 | 837.62 | 82 |
实施例8 | 28 | C<sub>57</sub>H<sub>42</sub>N<sub>2</sub>O | 770.98 | 770.33 | 81 |
实施例9 | 40 | C<sub>57</sub>H<sub>40</sub>N<sub>2</sub>O<sub>3</sub> | 800.96 | 800.61 | 83 |
实施例10 | 45 | C<sub>62</sub>H<sub>54</sub>N<sub>2</sub>O | 843.13 | 843.70 | 84 |
实施例11 | 51 | C<sub>59</sub>H<sub>48</sub>N<sub>2</sub>O | 801.05 | 801.25 | 80 |
实施例12 | 56 | C<sub>60</sub>H<sub>48</sub>N<sub>2</sub>O | 813.06 | 813.64 | 81 |
实施例13 | 60 | C<sub>53</sub>H<sub>44</sub>N<sub>2</sub>O | 724.95 | 724.81 | 83 |
实施例14 | 65 | C<sub>58</sub>H<sub>44</sub>N<sub>2</sub>O | 785.00 | 785.16 | 84 |
实施例15 | 68 | C<sub>63</sub>H<sub>47</sub>N<sub>3</sub> | 846.09 | 846.59 | 80 |
实施例16 | 72 | C<sub>56</sub>H<sub>43</sub>N<sub>3</sub> | 757.98 | 757.86 | 83 |
实施例17 | 78 | C<sub>63</sub>H<sub>51</sub>N<sub>3</sub> | 850.12 | 850.38 | 84 |
实施例18 | 85 | C<sub>62</sub>H<sub>56</sub>N<sub>2</sub>Si | 857.23 | 857.51 | 81 |
器件实施例1
本实施例提供一种绿光有机电致发光器件的制备方法,将本发明的化合物用作空穴传输层,按照通常的方法,制备有机电致发光元件。
将涂层厚度为150nm的ITO玻璃基板放在蒸馏水中清洗2次,超声波洗涤30分钟,用蒸馏水反复清洗2次,超声波洗涤10分钟,蒸馏水清洗结束后,异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥,转移到等离子体清洗机里,将上述基板洗涤5分钟,送到蒸镀机里。
将已经准备好的ITO透明电极上蒸镀厚度为30nm的HAT-CN作为空穴注入层;接着蒸镀60nm厚度的化合物1作为空穴传输层。上述空穴传输材料蒸镀结束后,制作OLED发光器件的发光层,其结构包括OLED发光层所使用CBP作为主体材料(比例为90%重量比),Ir(ppy)3作为掺杂材料,掺杂比例为10%重量比,发光层膜厚为40nm。
接着,在上述发光层上以10nm的厚度真空沉积BAlq来形成空穴阻挡层,在上述空穴阻挡层上以40nm的厚度真空沉积Alq3来形成电子输送层。然后,以0.2nm厚度的LiF来形成电子注入层,接着,以150nm的厚度沉积铝(Al)来形成阴极,由此,制备出有机电致发光元件。
器件结构:ITO/HAT-CN/化合物1/CBP:Ir(ppy)3/BAlq/Alq3/LiF/Al。
如上所述地完成OLED发光器件后,用公知的驱动电路将阳极和阴极连接起来,测量器件的电流效率以及器件的寿命。按照上述步骤完成电致发光器件的制作后,测量器件的驱动电压,发光效率和寿命。
相关材料的分子结构式如下所示:
器件实施例2-87
将器件实施例1中的化合物1分别置换为化合物2-87其他方法相同,分别制作含有化合物有机电致发光器件实施例2-器件实施例87。
器件比较例1
按照与实施例1相同的制备方法制备有机电致发光器件,其中,空穴传输层的化合物替换为比较化合物1:
器件比较例2
按照与实施例1相同的制备方法制备有机电致发光器件,其中,空穴传输层的化合物替换为比较化合物2:
器件比较例3
按照与实施例1相同的制备方法制备有机电致发光器件,其中,空穴传输层的化合物替换为比较化合物3:
试验例
测试器件实施例1-87和器件对比例1-3制备得到器件的性能,包括驱动电压、发光效率、寿命和相应的化合物的玻璃化转化温度,结果见表2。
测试方法:对制备的有机电致发光器件加以正向直流偏置电压,利用PhotoResearch公司的PR-650光度测量设备测定有机电致发光特性,亮度为8000cd/m2下利用McScience公司的寿命测定装置测定了T95的寿命。
表2制备得到器件的发光特性测试结果(亮度值为8000cd/m2)
从表2可以看出:与对比例相比,采用本发明实施例制备的化合物用于有机电致发光器件的空穴传输层,能够使器件具备更低的驱动电压,更好的发光效率,且器件的寿命也得到显著提升。
需要说明的是,本发明实施例中所制备的化合物与比较化合物2结构较为相似,都含有芴基,并且在芴基的9位存在取代基,存在芳胺侧链。与比较化合物2的区别在于:芳胺取代基的位置不同,本发明在芴基的9位存在芳胺基团和烷基,比较化合物芳胺基团在芴基的苯环上,且9位存在苯基取代。
通过测试数据可知:在性能上相对于器件比较例驱动电压下降在0.8~1.5V左右,发光效率提升7.9%~13.8%,器件寿命提高51~90h,玻璃化转变温度提高6-18℃。推测产生这种效果的原因在于:芳胺基团取代位置的不同,使材料的空间结构跟有利于空穴传输,同时在9位引入烷基修饰,提高玻璃化转变温度。
以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种有机电致发光化合物,其特征在于,其结构式为:
其中,a和b各自独立地表示0、1、2、3或4;c表示0、1、2或3;
X和Y各自独立地表示化学键、O、S、C(R4R5)、Si(R6R7)和NR8中的任意一种;
Ar1-Ar4和L1-L4各自独立地表示取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C10-C30)稠环基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6-C60)芳基胺基、取代或未取代的(C10-C30)螺环基,或与相邻取代基连接成单环或(C3-C30)脂肪族环或(C6-C30)芳香族环,或至少一个碳原子被置换为杂原子,所述杂原子选自氮、氧和硫中的任意一种;
R1-R3各自独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C3-C30)环烷基、取代或未取代的(C3-C30)杂环烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6~C60)芳基胺基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C60)芳氧基,或与相邻取代基连接形成单环或(C3-C30)多环脂肪族环或(C3-C30)芳香族环。
2.根据权利要求1所述的有机电致发光化合物,其特征在于,当X为化学键时,Y不为O;当Y为化学键时,X不为O;
优选地,X和Y与两侧的苯环形成的结构各自独立地选自以下基团中的任意一种:
其中,R4-R8各自独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C3-C30)环烷基、取代或未取代的(C3-C30)杂环烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C3-C30)杂芳基、取代或未取代的(C3-C30)杂芳基胺基、取代或未取代的(C6~C60)芳基胺基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C60)芳氧基,或与相邻取代基连接形成单环或(C3-C30)多环脂肪族环或(C3-C30)芳香族环;
优选地,a、b和c各自独立地表示0或1。
3.根据权利要求2所述的有机电致发光化合物,其特征在于,R1-R8各自独立地选自甲基、乙基、丙基、叔丁基、烷氧基、烷巯基、芳氧基、苯基、联苯基、萘基、二甲基芴基,二苯基芴基和螺环基中的任意一种;
优选地,R1-R8中至少一个碳原子被置换为杂原子,所述杂原子选自氮、氧和硫中的任意一种。
4.根据权利要求1所述的有机电致发光化合物,其特征在于,Ar1-Ar4和L1-L4各自独立地选自萘基、蒽基、菲基、苯并菲,苯基、咔唑基、叔丁基苯基、甲基苯基、三联苯基、联苯基、二苯并呋喃基、二苯并噻吩基、芴基和螺基及其衍生物中的任意一种。
7.根据权利要求6所述的制备方法,其特征在于,每步催化反应均控制反应温度为100-120℃,反应时间为8-12h;
优选地,所述反应物A-I和所述反应物B-I进行催化反应所采用的催化剂包括Pd2(dba)3、P(t-Bu)3和t-BuONa;
优选地,所述中间体C-I与所述反应物D-I进行催化反应所采用的催化剂包括Pd2(dba)3、P(t-Bu)3和t-BuONa;
优选地,所述中间体E-I和所述反应物F-I进行催化反应所采用的催化剂包括四(三苯基膦)钯和碳酸钾;
优选地,每步催化反应均是在保护气体氛围下进行反应。
8.根据权利要求7所述的制备方法,其特征在于,分离得到中间体C-I和中间体E-I的过程包括:将反应后的混合物进行过滤,将滤液和水混合分离有机相和水相,对水相进行萃取得到有机相,合并有机相进行洗脱纯化;
优选地,在进行洗脱纯化之前,对合并后的有机相进行干燥以去除溶剂;
优选地,所述洗脱纯化是采用二氯甲烷和石油醚的混合液作为洗脱剂,采用管柱色谱法进行纯化,二氯甲烷和石油醚的体积比为1:1-9;
优选地,在所述中间体E-I和所述反应物F-I进行催化反应之后进行冷却、过滤,对过滤得到的固体物料进行洗涤并干燥,再进行重结晶。
9.一种有机化合物功能层,其特征在于,其由权利要求1-5中任一项所述的有机电致发光化合物制备而得。
10.一种OLED发光器件,其特征在于,包括第一电极、第二电极和位于所述第一电极和所述第二电极之间的一个或多个有机化合物层,至少一个所述有机化合物层由权利要求1-5中任一项所述的有机电致发光化合物制备而得。
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