CN103992342B - Metallic aluminium coordination compound and application in an organic light emitting device thereof - Google Patents
Metallic aluminium coordination compound and application in an organic light emitting device thereof Download PDFInfo
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract description 65
- 239000004411 aluminium Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 90
- 239000010410 layer Substances 0.000 claims description 135
- 230000000903 blocking effect Effects 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000005525 hole transport Effects 0.000 claims description 15
- 239000002346 layers by function Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 62
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 62
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 58
- 238000000921 elemental analysis Methods 0.000 description 58
- 239000007787 solid Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 38
- 238000001308 synthesis method Methods 0.000 description 38
- 238000001704 evaporation Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 30
- 238000010992 reflux Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 230000008020 evaporation Effects 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000859 sublimation Methods 0.000 description 13
- 230000008022 sublimation Effects 0.000 description 13
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- -1 2, 3-dimethyl-8-hydroxy-1, 5-naphthyridine Chemical compound 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 6
- 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 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical group OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- FVIPZEZSEOZNTN-UHFFFAOYSA-N 5,6-dimethylpyridin-3-amine Chemical compound CC1=CC(N)=CN=C1C FVIPZEZSEOZNTN-UHFFFAOYSA-N 0.000 description 3
- UENBBJXGCWILBM-UHFFFAOYSA-N 6-methylpyridin-3-amine Chemical compound CC1=CC=C(N)C=N1 UENBBJXGCWILBM-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
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- 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 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- DUXUEYUDIQRWQO-UHFFFAOYSA-N 6-methyl-1h-1,5-naphthyridin-4-one Chemical compound N1C=CC(=O)C2=NC(C)=CC=C21 DUXUEYUDIQRWQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 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 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- YDMRDHQUQIVWBE-UHFFFAOYSA-N (2-hydroxyphenyl)boronic acid Chemical class OB(O)C1=CC=CC=C1O YDMRDHQUQIVWBE-UHFFFAOYSA-N 0.000 description 1
- HPDNGBIRSIWOST-UHFFFAOYSA-N 2-pyridin-2-ylphenol Chemical compound OC1=CC=CC=C1C1=CC=CC=N1 HPDNGBIRSIWOST-UHFFFAOYSA-N 0.000 description 1
- SHSQTJRJQHPJRQ-UHFFFAOYSA-N 4,6-dimethylpyridin-3-amine Chemical compound CC1=CC(C)=C(N)C=N1 SHSQTJRJQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- PUSLHPMAVSAWAP-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)NC2=CC(NC(C3=CC=CC=C3)C3=CC(C)=CC=C3)=CC(NC(C3=CC=CC=C3)C3=CC(C)=CC=C3)=C2)=C1 Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)NC2=CC(NC(C3=CC=CC=C3)C3=CC(C)=CC=C3)=CC(NC(C3=CC=CC=C3)C3=CC(C)=CC=C3)=C2)=C1 PUSLHPMAVSAWAP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer 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
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention provides a kind of metallic aluminium coordination compound, there is structural formula as shown in the formula (I).Wherein, Q is selected from the structural formula shown in formula (Q1) or formula (Q2)；R1For methyl, R2-R6Independently selected from one of them of hydrogen atom, methyl or cyano group；L is the structural formula shown in formula (IV)；R7-R11One of them of nitrogen-containing hetero aromatic ring independently selected from hydrogen atom, phenyl, pyridine groups, pyrimidine group, the substituted or non-substituted aromatic ring of C6 ~ C30 or C6 ~ C30.Present invention also offers a kind of organic electroluminescence device containing described metallic aluminium coordination compound.The electron mobility of this metallic aluminium coordination compound is high, can as luminescent layer material of main part, hole barrier layer material or electron transport layer materials are in OLED, it is achieved that the multifunction of homogenous material, and simplify device architecture, it is achieved that the high efficiency of device and low-voltage.
Description
Technical Field
The invention relates to a novel organic luminescent material and application thereof in an organic luminescent device. In particular to a metallic aluminum complex and an organic electroluminescent device containing the material.
Background
In 1987, Dengqing cloud (C.W.Tang) and VanSlyke of Kodak corporation reported the use of tris (8-hydroxyquinoline) aluminum (Alq)3) As an organic functional layer, organic electroluminescent devices (OLEDs) are successfully prepared under low voltage for the first time, and the hot research of organic materials applied to the field of electroluminescence is stimulated. The organometallic aluminum complex is widely developed and applied to OLEDs as an electron transport layer or a main light emitting layer because of its good thermal stability, easy deposition into a non-cavity thin film under vacuum, simple synthesis process, low cost and the like.
The hole mobility of the currently commonly used hole transport materials is generally 10-5～10-3cm2V.s, e.g. hole mobility of 1 x 10 for TPD-3cm2V · s. The electron mobility of the electron transport material is generally 10-6～10-4cm2V. s, e.g.Alq3 electron mobility was only 4.7 x 10-6cm2V · s, and the cationic instability of Alq3 affects the lifetime of the device (Science, 1999,283,1900). The electron mobility of the commonly used electron transport material Bebq2 is better (10)-4cm2V · s), but Bebq2 is highly toxic (appl. phys. lett.2008,92,113308). Currently, although electron transport materials with high electron mobility are still being developed and reported (chem. mater.2011,23,621), there is a need to develop electron transport materials with high electron mobility and high stability that can be really applied in practice.
Since the phosphorescent material may utilize 75% of triplet excitons and 25% of singlet excitons, and the fluorescent material may utilize only 25% of singlet excitons, the electrophosphorescent device has higher luminous efficiency than the electroluminescent device. In a typical phosphorescent OLED device, a phosphorescent dye is not used as a light emitting layer alone, but is doped in a suitable host material to form a host-guest light emitting system to weaken the concentration quenching effect of triplet excitons. The triplet energy level of the host material used is higher than that of the dye, so that triplet excitons can be confined in the light-emitting layer. The host material generally used is a hole transporting type material, and an electron transporting type material is also used. Forrest et al Ir (ppy)3When the material BCP with the electron transport performance and the hole blocking performance is doped to be used as a main light-emitting layer, and a hole blocking layer is not used in the device, the fact that excitons of the device can be limited in the light-emitting layer after the thickness of the light-emitting layer is optimized is found, the external quantum efficiency of the device is 15.4%, but the service life of the device is not long (appl.Phys.Lett.,2000,77, 904). The Japanese pioneer company also published that the electronic transmission performance BAlq is used as a main material and a hole blocking material of a red phosphorescent device in the SID conference, the device efficiency can reach 8.6 percent, and the device has long service life which can reach 30000 hours. However, the triplet energy level of the BAlq material is only 2.3eV, and when the BAlq material is used as a host, the BAlq material can only be used in a red phosphorescent OLED, the electron mobility is not high, and the efficiency of the device is not good enough. To achieve efficient, stable, simplified green and blue phosphorescent devices, higher triplet energy levels and high electron mobility or dual emission are soughtA polar host material.
Compared with fluorescent devices, the triplet excitons of phosphorescent devices have a long lifetime and are easily diffused to other layers, resulting in reduced device efficiency and impure light color, and therefore hole blocking materials with energy gaps larger than the energy of the excitons are often required to be introduced into the light emitting layer and the electron transport layer to confine the triplet excitons in the light emitting layer. The hole blocking materials commonly used at present comprise pure organic substances such as BCP, BPhen and TPBi and metal complexes such as PALq and BALq. Ir (ppy) using pure organic TPBi as hole blocking layer3Phosphor device with luminance of 500cd/m2When using an Ir (ppy) with BALq as the barrier layer, the efficiency can reach 25.3cd/A, but the device lifetime is only 70 hours3The device can improve the service life of the device (up to 10000 hours), but the efficiency of the device is 19.0cd/A (appl. Phys. Lett.2002,81,162). This is because the HOMO energy level of BAlq is not as low as TPBi, and exciton blocking may not be complete. BCP, BPhen, BALq, etc. have triplet energy levels of less than 2.65eV, and exciton energy is easily quenched when used in a blue phosphorescent device. Therefore, the search for a hole blocking material with high stability, high triplet energy level and low HOMO energy level is very important for realizing efficient and stable blue phosphorescent devices and white OLED devices.
Disclosure of Invention
The invention aims to solve the problem that a long-life transmission material and a main body material with high electron mobility are lacked, so that a metal aluminum complex with high electron mobility, low HOMO energy level and higher triplet state energy level is provided; the material is applied to functional layers of organic electroluminescent devices, such as a main light emitting layer, a hole blocking layer or an electron transport layer, so that the multifunction of a single material is realized, the structure of the device is simplified, and the high efficiency and the low voltage of the device are realized.
The invention is based on the above consideration, and from the perspective of molecular design, the electron transport capacity and the hole blocking capacity of the material are improved by introducing electron-withdrawing groups such as pyridine, pyrimidine and the like on the auxiliary ligand L, so as to obtain high-efficiency electron transport materials and hole blocking materials. Meanwhile, an electron-withdrawing N atom can be introduced to the 5-position of the main ligand Q to reduce the charge transfer in molecules, so that the triplet state energy level of the material is improved while the material has good thermal stability and chemical stability, and the application of the material as a main material in a blue phosphorescent device is realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a metal aluminum complex having a structural formula as shown in formula (I):
(Q)2-Al-O-L
（I）
wherein,
q is selected from structural formulas shown as a formula (Q1), a formula (Q2), a formula (Q3) or a formula (Q4);
R1is methyl, R2-R6Independently selected from one of a hydrogen atom, a methyl group or a cyano group;
l is a structural formula shown in formula (IV):
R7-R11independently selected from one of hydrogen atoms, phenyl, pyridine groups, pyrimidine groups, substituted or unsubstituted aromatic rings of C6-C30 or nitrogen-containing heteroaromatic rings of C6-C30.
The compound has the following structural formula:
the metal aluminum complex is used as a luminescent layer material, an electron transport layer material or a hole blocking layer material in an organic electroluminescent device.
An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is one or a combination of a plurality of hole injection layers, hole transport layers, electron blocking layers, light emitting layers, hole blocking layers, electron transport layers and electron injection layers, and the light emitting layer is made of one or a plurality of metal aluminum complexes.
An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is one or a combination of a plurality of hole injection layers, hole transport layers, electron blocking layers, light emitting layers, hole blocking layers, electron transport layers and electron injection layers, and the electron transport layer is made of one or a plurality of metal aluminum complexes.
An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is a combination of one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer is made of one or more metal aluminum complexes.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the material synthesized by the invention has good stability and high electron mobility, and can be used as an electron transport material as shown in example fifty-nine: the material is used as an electron transport layer of a red phosphorescent device, the lighting voltage of the material is lower than that of a corresponding device using BALq as the electron transport layer, and the power efficiency is improved; as a host material of the light-emitting layer, as shown in example sixty: the material of the invention is used as the main luminescent layer of the blue phosphorescent device, and has good color purity, high power efficiency and long service life of the device. This material acts as a hole blocking layer material, as shown in example sixty one: the material of the invention is used as an electron transport layer of a green phosphorescent device, and has low lighting voltage and high power efficiency. The invention realizes the multifunction of a single material and simultaneously realizes the high efficiency and the long service life of the device.
Drawings
FIG. 1 is a graph of current density versus voltage, luminance versus voltage for devices-1, OLED-2, OLED-3, which are comparative to devices of embodiments of the present invention.
FIG. 2 is a graph of power efficiency versus current density for example devices of the present invention versus devices-1, OLED-2, OLED-3.
FIG. 3 is a nuclear magnetic resonance spectrum of ligand L:2, 6-dipyridyl phenol of the example of the present invention.
FIG. 4 is a nuclear magnetic resonance spectrum of material Q1-7 of an example of the present invention.
FIG. 5 is a MALDI-TOF-MS mass spectrum of Q1-7, an example material of the present invention.
The specific implementation mode is as follows:
the ligand Q1 of the present invention is directly available. Ligand Q2 synthesis of 2-methyl-8-hydroxy-1, 5-naphthyridine ligand can be prepared according to the following route, with reference to the literature (j.am. chem. soc.2009,131, 763-777).
The reaction formula is as follows:
the process is as follows: the synthesis is carried out in two steps. First 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl orthoformate and stirred under reflux for 2 hours. After cooling to room temperature, 0.38g (3.5mmol) of 2-methyl-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 50%.
1.6g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 60% yield.
Different ligands can be obtained starting from 2, 3-dimethyl-5-aminopyridine and substituted 2, 3-dimethyl-5-aminopyridines. The ligands belonging to formula Q2 are all obtained by the above route.
The ligand L of the present invention, 2-pyridylphenol, was synthesized according to the following scheme, with reference to the literature (U.S. Pat. No. 4, 20110039958, 1).
The reaction formula is as follows:
the process is as follows: the composition is carried out in three steps. First, 0.72g (30mmol) of sodium hydride and 50ml of tetrahydrofuran were placed in a three-necked flask, and 5.2g (30mmol) of benzyl bromide was added dropwise. When the reaction mixture did not generate any more bubbles, 1.38g (8mmol) of 2-bromophenol was added to the reaction mixture. The reaction was stirred under heating and reflux for 10 hours. The reaction solution was cooled and a small amount of water was added to the solution to quench the excess sodium hydride. Extracting the reaction solution with water and dichloromethane, separating to obtain an organic phase, drying, filtering, and spin-drying the solvent. Separating by column chromatography, and eluting with petroleum ether to obtain white solid with yield of 95%.
Then, 0.78g (3mmol) of the obtained solid product, 0.406g (3.3 mmol) of 3-pyridineboronic acid and 0.102g (0.1mmol) of tetrakis (triphenylphosphine) palladium were dissolved in 9ml of a mixed solution of 2M potassium carbonate and 15ml of N, N-dimethylformamide. The reaction was stirred with heating for 48 hours under nitrogen. After the reaction had stopped, the organic phase was extracted with dichloromethane, dried, filtered and the solvent was spin-dried. Column chromatography with ethyl acetate/ethanol =10/1 as eluent gave finally a beige solid in 60% yield.
Finally, 2.6g (10mmol) of the solid obtained above was dissolved in 100ml of methanol, and 0.4g of palladium on carbon was added as a catalyst, and the reaction was stirred under a hydrogen atmosphere for 24 hours. The catalyst is removed by filtration while the solution is hot, and the final product 2- (3-pyridine) phenol can be obtained by spin-drying the solvent.
Different ligands can be obtained by using bromophenol and corresponding pyridine boronic acid or brominated pyrimidine and substituted hydroxyphenylboronic acid according to the reaction path. The ligands belonging to the general formula L are all obtained by the above route.
Synthesis example of the Metal Complex of the present invention:
the first embodiment is as follows: compound Q1-1
The reaction formula is as follows:
4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of 4- (3-pyridine) phenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Then 20ml toluene dissolved 2-methyl-8-hydroxy quinoline, the solution was added to the reaction flask, the solution was heated and stirred reflux reaction overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.3g of a yellowish solid with a yield of 42%.
1H-NMR(CDCl3,300MHz,[ppm]):2.73(s,6H),6.79~6.81(d,2H),6.89~6.92(m,2H),7.19~7.20(d,4H),7.37~7.39(m,4H),7.60~7.62(d,2H),7.89~7.92(d,2H),8.65~8.67(d,2H).
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.37;H,4.36;N,8.36.
Example two: compound Q1-2
The 3- (3-pyridine) phenol ligand was synthesized according to the reference (U.S. Pat. No. 4, 20110039958, 1). Synthesis of the complex the synthesis procedure of example one was followed with a yield of 45%.
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.44;H,4.55;N,8.00.
Example three: compound Q1-3
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2- (3-pyridine) phenol. The yield was 42%.
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.37;H,4.36;N,8.36.
Example four: compound Q1-4
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 4- (4-pyridine) phenol. The yield was 44%.
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.37;H,4.36;N,8.36.
Example five: compound Q1-5
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 3- (4-pyridine) phenol. The yield was 43%.
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.37;H,4.36;N,8.36.
Example six: compound Q1-6
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2- (4-pyridine) phenol. The yield was 43%.
ESI-MS[m/z]:514[M+H]+Elemental analysis (C)31H24AlN3O3）：Anal.Calcd.:C,72.53;H,4.71;N,8.18.Found:C,72.37;H,4.36;N,8.36.
Example seven: compound Q1-7
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:591[M+H]+Elemental analysis (C)36H27AlN4O3）：Anal.Calcd.:C,73.21;H,4.61;N,9.49.Found:C,73.37;H,4.50;N,9.53.
Example eight: compound Q1-8
The synthesis method is the same as that of example one, except that 4- (3-pyridine) phenol is replaced by 2, 6-di (4-pyridine) phenol. The yield was 48%.
ESI-MS[m/z]:591[M+H]+Elemental analysis (C)36H27AlN4O3）：Anal.Calcd.:C,73.21;H,4.61;N,9.49.Found:C,73.11;H,4.71;N,9.36.
Example nine: compound Q1-9
The synthesis method is the same as that of example one, except that 4- (3-pyridine) phenol is replaced by 3, 5-di (4-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:591[M+H]+Elemental analysis (C)36H27AlN4O3）：Anal.Calcd.:C,73.21;H,4.61;N,9.49.Found:C,73.37;H,4.50;N,9.53.
Example ten: compound Q1-10
The synthesis method is the same as that of example one, except that 4- (3-pyridine) phenol is replaced by 3, 5-di (3-pyridine) phenol. The yield was 41.
ESI-MS[m/z]:591[M+H]+Elemental analysis (C)36H27AlN4O3）：Anal.Calcd.:C,73.21;H,4.61;N,9.49.Found:C,73.40;H,4.48;N,9.45.
Example eleven: compound Q1-11
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2,4, 6-tri (3-pyridine) phenol. The yield was 41%.
ESI-MS[m/z]:668[M+H]+Elemental analysis (C)41H30AlN5O3）：Anal.Calcd.:C,73.75;H,4.53;N,10.49.Found:C,73.61;H,4.71;N,10.36.
Example twelve: compound Q1-12
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2,4, 6-tri (4-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:668[M+H]+Elemental analysis (C)41H30AlN5O3）：Anal.Calcd.:C,73.75;H,4.53;N,10.49.Found:C,73.50;H,4.60;N,10.53.
Example thirteen: compound Q1-13
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 4- (3-pyrimidine) phenol. The yield was 48%.
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)30H23AlN4O3）：Anal.Calcd.:C,70.03;H,4.51;N,10.89.Found:C,70.13;H,4.36;N,11.00.
Example fourteen: compound Q1-14
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 3- (3-pyrimidine) phenol. The yield was 45%.
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)30H23AlN4O3）：Anal.Calcd.:C,70.03;H,4.51;N,10.89.Found:C,70.18;H,4.44;N,10.86.
Example fifteen: compound Q1-15
The synthesis method is the same as the first example, except that 4- (3-pyridine) phenol is replaced by 2- (3-pyrimidine) phenol. The yield was 41%.
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)30H23AlN4O3）：Anal.Calcd.:C,70.03;H,4.51;N,10.89.Found:C,70.10;H,4.46;N,10.96.
Example sixteen: compound Q1-16
The synthesis method is the same as that of example one, except that 4- (3-pyridine) phenol is replaced by 2, 6-di (3-pyrimidine) phenol. The yield was 40%.
ESI-MS[m/z]:593[M+H]+Elemental analysis (C)34H25AlN6O3）：Anal.Calcd.:C,68.91;H,4.25;N,14.18.Found:C,68.99;H,4.42;N,14.20.
Example seventeen: compound Q1-17
4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of 4- (3-pyridine) phenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Then 20ml toluene dissolved 2, 4-two methyl 8-hydroxy quinoline, the solution is added to the reaction flask, the solution is heated and stirred reflux reaction overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.5g of a yellowish solid with a yield of 44%.
1H-NMR(CDCl3,300MHz,[ppm]):2.55(s,6H),2.73(s,6H),6.79~6.81(d,2H),6.89~6.92(m,4H),7.19~7.20(d,2H),7.30~7.32(d,2H),7.40~7.42(m,3H),7.89~7.92(d,1H),8.65~8.67(d,2H).
ESI-MS[m/z]:542[M+H]+Elemental analysis (C)33H28AlN3O3）：Anal.Calcd.:C,73.19;H,5.21;N,7.76.Found:C,73.10;H,5.42;N,7.56.
Example eighteen: compound Q1-18
The synthesis method is the same as that of the seventeenth embodiment, except that 4- (3-pyridine) phenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)32H27AlN2O3）：Anal.Calcd.:C,74.69;H,5.29;N,5.44.Found:C,74.89;H,5.16;N,5.33.
Example nineteenth: compound Q1-19
The synthesis method is the same as that of example seventeen, except that 4- (3-pyridine) phenol is replaced by 4- (4-pyridine) phenol. The yield was 46%.
ESI-MS[m/z]:542[M+H]+Elemental analysis (C)33H28AlN3O3）：Anal.Calcd.:C,73.19;H,5.21;N,7.76.Found:C,73.26;H,5.13;N,7.73.
Example twenty: compound Q1-20
The synthesis method is the same as that of the seventeenth embodiment, except that 4- (3-pyridine) phenol is replaced by beta-naphthol. The yield was 42%.
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)32H27AlN2O3）：Anal.Calcd.:C,74.69;H,5.29;N,5.44.Found:C,74.54;H,5.33;N,5.25.
Example twenty one: compound Q1-21
The synthesis method is the same as that of example seventeen, except that 4- (3-pyridine) phenol is replaced by 2,4, 6-tri (3-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:696[M+H]+Elemental analysis (C)43H34AlN5O3）：Anal.Calcd.:C,74.23;H,4.93;N,10.07.Found:C,74.45;H,4.76;N,10.11.
Example twenty two: compound Q1-22
The synthesis method is the same as that of example seventeen, except that 4- (3-pyridine) phenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 46%.
ESI-MS[m/z]:619[M+H]+Elemental analysis (C)38H31AlN4O3）：Anal.Calcd.:C,73.77;H,5.05;N,9.06.Found:C,73.68;H,5.22;N,9.01.
Example twenty three: compound Q1-23
The synthesis method is the same as that of example seventeen, except that 4- (3-pyridine) phenol is replaced by 2,4, 6-tri (4-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:696[M+H]+Elemental analysis (C)43H34AlN5O3）：Anal.Calcd.:C,74.23;H,4.93;N,10.07.Found:C,74.15;H,4.88;N,10.117.
Example twenty-four: compound Q1-24
The synthesis method is the same as that of example seventeen, except that 4- (3-pyridine) phenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 46%.
ESI-MS[m/z]:619[M+H]+Elemental analysis (C)38H31AlN4O3）：Anal.Calcd.:C,73.77;H,5.05;N,9.06.Found:C,73.59;H,5.01;N,9.19.
Example twenty-five: compound Q2-1
First 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl orthoformate and stirred under reflux for 2 hours. After cooling to room temperature, 0.38g (3.5mmol) of 2-methyl-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 50%.
1.6g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 60% yield.
Finally, 4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of biphenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Two equivalents of 2-methyl-8-hydroxy-1, 5-naphthyridine were dissolved in 20ml of toluene, the solution was added dropwise to a reaction flask, and the solution was heated with stirring and refluxed overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.3g of a yellowish solid with a yield of 44%.
1H-NMR(CDCl3,300MHz,[ppm]):2.77(s,6H),6.79~6.81(d,2H),7.05~7.07(m,2H),7.22(s,1H),7.31~7.33(m,4H),7.46~7.48(d,2H),7.51~7.53(d,2H),8.39~8.41(d,2H),8.80~8.82(d,2H).
ESI-MS[m/z]:515[M+H]+Elemental analysis (C)30H23AlN4O3）：Anal.Calcd.:C,70.03;H,4.51;N,10.89.Found:C,70.09;H,4.47;N,10.93.
Example twenty-six: compound Q2-2
The synthesis method is the same as twenty-five of the example, except that the diphenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:489[M+H]+Elemental analysis (C)28H21AlN4O3）：Anal.Calcd.:C,68.85;H,4.33;N,11.47.Found:C,68.91;H,4.42;N,11.20.
Example twenty-seven: compound Q2-3
The synthesis was the same as twenty-five of the example except that the diphenols were replaced with 2, 6-diphenylphenol. The yield was 48%.
ESI-MS[m/z]:591[M+H]+Elemental analysis (C)36H27AlN4O3）：Anal.Calcd.:C,73.21;H,4.61;N,9.49.Found:C,73.11;H,4.42;N,9.61.
Example twenty-eight: compound Q2-4
The synthesis was performed as in twenty-five of the examples, except that the diphenols were replaced with 4- (3-pyridine) phenol. The yield was 43%.
ESI-MS[m/z]:516[M+H]+Elemental analysis (C)29H22AlN5O3）：Anal.Calcd.:C,67.57;H,4.30;N,13.59.Found:C,67.63;H,4.22;N,13.40.
Example twenty-nine: compound Q2-5
The synthesis was performed as in twenty-five of the examples, except that the diphenols were replaced with 4- (4-pyridine) phenol. The yield was 45%.
ESI-MS[m/z]:516[M+H]+Elemental analysis (C)29H22AlN5O3）：Anal.Calcd.:C,67.57;H,4.30;N,13.59.Found:C,67.53;H,4.28;N,13.54.
Example thirty: compound Q2-6
The synthesis was performed as in twenty-five of the example except that the diphenols were replaced with 3- (3-pyridine) phenol. Yield 46.
ESI-MS[m/z]:516[M+H]+Elemental analysis (C)29H22AlN5O3）：Anal.Calcd.:C,67.57;H,4.30;N,13.59.Found:C,67.66;H,4.25;N,13.47.
Example thirty one: compound Q2-7
The synthesis method is the same as twenty-five of the example, except that the diphenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 45%.
ESI-MS[m/z]:593[M+H]+Elemental analysis (C)34H25AlN6O3）：Anal.Calcd.:C,68.91;H,4.25;N,14.18.Found:C,68.99;H,4.42;N,14.20.
Example thirty-two: compound Q2-8
The synthesis method is the same as twenty-five of the example, except that the diphenol is replaced by 2, 6-di (4-pyridine) phenol. The yield was 43%.
ESI-MS[m/z]:593[M+H]+Elemental analysis (C)34H25AlN6O3）：Anal.Calcd.:C,68.91;H,4.25;N,14.18.Found:C,68.86;H,4.36;N,14.10.
Example thirty-three: compound Q2-9
The synthesis method is the same as twenty-five of the example, except that the diphenol is replaced by 2,4, 6-tri (4-pyridine) phenol. The yield was 41%.
ESI-MS[m/z]:670[M+H]+Elemental analysis (C)39H28AlN7O3）：Anal.Calcd.:C,69.95;H,4.21;N,14.64.Found:C,69.63;H,4.22;N,14.40.
Example thirty-four: compound Q2-10
The synthesis method is the same as twenty-five of the example, except that the diphenol is replaced by 2,4, 6-tri (3-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:670[M+H]+Elemental analysis (C)39H28AlN7O3）：Anal.Calcd.:C,69.95;H,4.21;N,14.64.Found:C,69.83;H,4.12;N,14.50.
Example thirty-five: compound Q2-11
First 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl orthoformate and stirred under reflux for 2 hours. After cooling to room temperature, 0.43g (3.5mmol) of 2, 3-dimethyl-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 50%.
1.66g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 57% yield.
Finally, 4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of biphenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Two equivalents of 2, 3-dimethyl-8-hydroxy-1, 5-naphthyridine were dissolved in 20ml of toluene, the solution was added dropwise to a reaction flask, and the solution was heated with stirring and refluxed overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.5g of a yellowish solid with a yield of 41%.
1H-NMR(CDCl3,300MHz,[ppm]):2.44(s,6H),2.77(s,6H),6.79~6.81(d,2H),6.89~6.92(m,2H),7.22(s,1H),7.33~7.35(d,4H),7.37~7.39(m,2H),8.34(s,2H),8.65~8.67(d,2H).
ESI-MS[m/z]:543[M+H]+Elemental analysis (C)32H27AlN4O3）：Anal.Calcd.:C,70.84;H,5.02;N,10.23.Found:C,70.49;H,5.21;N,10.33.
Example thirty-six: compound Q2-12
The synthesis method is the same as thirty-five of the example, except that the diphenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:517[M+H]+Elemental analysis (C)30H25AlN4O3）：Anal.Calcd.:C,69.76;H,4.88;N,10.85.Found:C,69.63;H,4.67;N,10.98.
Example thirty-seven: compound Q2-13
The synthesis method is the same as thirty-five of the example, except that the diphenol is replaced by 2, 6-diphenylphenol. The yield was 41%.
ESI-MS[m/z]:619[M+H]+Elemental analysis (C)38H31AlN4O3）：Anal.Calcd.:C,73.77;H,5.05;N,9.06.Found:C,73.66;H,5.16;N,8.98.
Example thirty-eight: compound Q2-14
The synthesis was carried out as in example thirty-five except that the diphenols were replaced with 4- (4-pyridine) phenol. The yield was 39%.
ESI-MS[m/z]:544[M+H]+Elemental analysis (C)31H26AlN5O3）：Anal.Calcd.:C,68.50;H,4.82;N,12.88.Found:C,68.63;H,4.67;N,12.98.
Example thirty-nine: compound Q2-15
The synthesis method is the same as thirty-five of the example, except that the diphenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 44%.
ESI-MS[m/z]:621[M+H]+Elemental analysis (C)36H29AlN6O3）：Anal.Calcd.:C,69.67;H,4.71;N,13.54.Found:C,69.63;H,4.88;N,13.64.
Example forty: compound Q2-16
The synthesis method is the same as thirty-five of the example, except that the diphenol is replaced by 2,4, 6-tri (3-pyridine) phenol. The yield was 42%.
ESI-MS[m/z]:698[M+H]+Elemental analysis (C)41H32AlN7O3）：Anal.Calcd.:C,70.58;H,4.62;N,14.05.Found:C,70.33;H,4.67;N,14.08.
Example forty one: compound Q2-17
First 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl orthoformate and stirred under reflux for 2 hours. After cooling to room temperature, 0.43g (3.5mmol) of 2, 4-dimethyl-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 46%.
1.66g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 55% yield.
Finally, 4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of biphenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Two equivalents of 2, 4-dimethyl-8-hydroxy-1, 5-naphthyridine were dissolved in 20ml of toluene, the solution was added dropwise to a reaction flask, and the solution was heated with stirring and refluxed overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.3g of a yellowish solid with a yield of 39%.
1H-NMR(CDCl3,300MHz,[ppm]):2.48(s,6H),2.77(s,6H),6.79~6.81(d,2H),6.89~6.92(m,2H),7.22(s,1H),7.33~7.35(d,4H),7.37~7.39(m,2H),8.34(s,2H),8.65~8.67(d,2H).
ESI-MS[m/z]:543[M+H]+Elemental analysis (C)32H27AlN4O3）：Anal.Calcd.:C,70.84;H,5.02;N,10.23.Found:C,70.49;H,5.21;N,10.33.
Example forty two: compound Q2-18
The synthesis method is the same as example forty one, except that the diphenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:517[M+H]+Elemental analysis (C)30H25AlN4O3）：Anal.Calcd.:C,69.76;H,4.88;N,10.85.Found:C,69.80;H,4.67;N,10.98.
Example forty-three: compound Q2-19
The synthesis was performed as in example forty one except that the diphenols were replaced with 4- (4-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:544[M+H]+Elemental analysis (C)31H26AlN5O3）：Anal.Calcd.:C,68.50;H,4.82;N,12.88.Found:C,68.53;H,4.76;N,12.86.
Example forty-four: compound Q2-20
The synthesis was performed as in example forty one except that the diphenols were replaced with 2, 6-diphenylphenol. The yield was 38%.
ESI-MS[m/z]:619[M+H]+Elemental analysis (C)38H31AlN4O3）：Anal.Calcd.:C,73.77;H,5.05;N,9.06.Found:C,73.78;H,5.11;N,9.13.
Example forty-five: compound Q2-21
The synthesis method is the same as example forty one, except that the diphenol is replaced by 2,4, 6-tri (3-pyridine) phenol. The yield was 44%.
ESI-MS[m/z]:698[M+H]+Elemental analysis (C)41H32AlN7O3）：Anal.Calcd.:C,70.58;H,4.62;N,14.05.Found:C,70.55;H,4.70;N,14.08.
Example forty-six: compound Q2-22
The synthesis method is the same as example forty one, except that the diphenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 42%.
ESI-MS[m/z]:621[M+H]+Elemental analysis (C)36H29AlN6O3）：Anal.Calcd.:C,69.67;H,4.71;N,13.54.Found:C,69.76;H,4.63;N,13.70.
Example forty-seven: compound Q2-23
First, 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl acetate, and the mixture was stirred under reflux for 2 hours. After cooling to room temperature, 0.43g (3.5mmol) of 2-methyl-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 46%.
1.66g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 57% yield.
Finally, 4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of biphenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Two equivalents of 2, 6-dimethyl-8-hydroxy-1, 5-naphthyridine were dissolved in 20ml of toluene, the solution was added dropwise to a reaction flask, and the solution was heated with stirring and refluxed overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.35g of a yellowish solid with a yield of 40%.
1H-NMR(CDCl3,300MHz,[ppm]):2.77(s,12H),6.79~6.81(d,2H),6.89~6.92(m,2H),7.22(s,1H),7.33~7.35(d,4H),7.37~7.39(m,2H),8.34(s,2H),8.65~8.67(d,2H).
ESI-MS[m/z]:543[M+H]+Elemental analysis (C)32H27AlN4O3）：Anal.Calcd.:C,70.84;H,5.02;N,10.23.Found:C,70.51;H,5.19;N,10.03.
Example forty-eight: compound Q2-24
The synthesis method is the same as example forty-seven, except that the diphenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:517[M+H]+Elemental analysis (C)30H25AlN4O3）：Anal.Calcd.:C,69.76;H,4.88;N,10.85.Found:C,69.86;H,4.76;N,10.65.
Example forty-nine: compound Q2-25
The synthesis was performed as in example forty-seven, except that the diphenols were replaced with 4- (4-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:544[M+H]+Elemental analysis (C)31H26AlN5O3）：Anal.Calcd.:C,68.50;H,4.82;N,12.88.Found:C,68.58;H,4.78;N,12.77.
Example fifty: compound Q2-26
The synthesis was performed as in example forty-seven, except that the diphenols were replaced with 2, 6-diphenylphenol. The yield was 41%.
ESI-MS[m/z]:619[M+H]+Elemental analysis (C)38H31AlN4O3）：Anal.Calcd.:C,73.77;H,5.05;N,9.06.Found:C,73.86;H,5.00;N,9.03.
Example fifty one: compound Q2-27
The synthesis was performed as in example forty-seven, except that the diphenols were replaced with 2,4, 6-tris (3-pyridinol). The yield was 44%.
ESI-MS[m/z]:698[M+H]+Elemental analysis (C)41H32AlN7O3）：Anal.Calcd.:C,70.58;H,4.62;N,14.05.Found:C,70.66;H,4.70;N,14.00.
Example fifty two: compound Q2-28
The synthesis method is the same as example forty-seven except that the diphenol is replaced by 2, 6-di (3-pyridine) phenol. The yield was 42%.
ESI-MS[m/z]:621[M+H]+Elemental analysis (C)36H29AlN6O3）：Anal.Calcd.:C,69.67;H,4.71;N,13.54.Found:C,69.80;H,4.63;N,13.60.
Example fifty three: compound Q2-29
First 0.6g (4 mmol) of a solid of cycloisopropyl malonate was dissolved in 6ml (36 mmol) of triethyl orthoformate and stirred under reflux for 2 hours. After cooling to room temperature, 0.43g (3.5mmol) of 2-methyl-4-cyano-5-aminopyridine was added to the reaction mixture, and the reaction was continued under reflux for 2 hours. The resulting solution was concentrated and separated by column chromatography using ethyl acetate/dichloromethane =1/1 as eluent to give an off-white solid powder with a yield of 46%.
1.66g (6mmol) of the solid product obtained are subsequently dissolved in 100ml of diphenyl ether and stirred under reflux under nitrogen for 2 hours. The reaction solution was filtered to give a grey solid. The product was purified by zone sublimation to give a white solid at 57% yield.
Finally, 4.1g (20mmol) of aluminum isopropoxide and 3.42g (20mmol) of biphenol were dissolved in 80ml of toluene, and the reaction was stirred at reflux for 3 hours. Two equivalents of 2-methyl-4-cyano-8-hydroxy-1, 5-naphthyridine were dissolved in 20ml of toluene, the solution was added dropwise to a reaction flask, and the solution was heated with stirring and refluxed overnight. Filtered and washed with toluene to give a white flocculent solid. The final product was purified by zone sublimation to give 4.35g of a yellowish solid with a yield of 40%.
1H-NMR(CDCl3,300MHz,[ppm]):2.77(s,6H),6.79~6.81(d,2H),7.05~7.07(m,2H),7.22(s,1H),7.33~7.35(d,4H),7.47~7.49(m,2H),8.11(s,2H),8.83~8.85(d,2H).
ESI-MS[m/z]:565[M+H]+Elemental analysis (C)32H21AlN6O3）：Anal.Calcd.:C,68.08;H,3.75;N,14.89.Found:C,68.21;H,3.63;N,14.83.
Example fifty-four: compound Q2-30
The synthesis method is the same as that of fifty-three in the example, except that the diphenol is replaced by alpha-naphthol. The yield was 40%.
ESI-MS[m/z]:539[M+H]+Elemental analysis (C)30H19AlN6O3）：Anal.Calcd.:C,66.91;H,3.56;N,15.61.Found:C,66.80;H,3.63;N,15.60.
Example fifty-five: compound Q2-31
The synthesis was performed as in example fifty-three, except that the diphenol was replaced with 4- (4-pyridine) phenol. The yield was 42%.
ESI-MS[m/z]:566[M+H]+Elemental analysis (C)31H20AlN7O3）：Anal.Calcd.:C,65.84;H,3.56;N,17.34.Found:C,66.00;H,3.43;N,17.50.
Example fifty-six: compound Q2-32
The synthesis was performed as in example fifty-three, except that biphenol was replaced by 2, 6-diphenylphenol. The yield was 41%.
ESI-MS[m/z]:641[M+H]+Elemental analysis (C)38H25AlN6O3）：Anal.Calcd.:C,71.24;H,3.93;N,13.12.Found:C,71.13;H,3.86;N,13.21.
Example fifty-seven: compound Q2-33
The synthesis method is the same as that of example fifty-three except that the diphenol is replaced by 2,4, 6-tris (3-pyridine) phenol. The yield was 40%.
ESI-MS[m/z]:720[M+H]+Elemental analysis (C)41H26AlN9O3）：Anal.Calcd.:C,68.42;H,3.64;N,17.52.Found:C,68.31;H,3.76;N,17.41.
Example fifty-eight: compound Q2-34
The synthesis method is the same as that of example fifty-three except that the diphenol is replaced by 2, 6-bis (3-pyridine) phenol. The yield was 39%.
ESI-MS[m/z]:641[M+H]+Elemental analysis (C)36H23AlN8O3）：Anal.Calcd.:C,67.29;H,3.61;N,17.44.Found:C,67.33;H,3.82;N,17.21.。
The following are examples of the use of the compounds of the present invention:
preferred embodiments for preparing an organic light emitting device:
the typical structure of an OLED device is: substrate/anode/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/cathode.
(1) The substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. The substrate is transparent, waterproof, has a smooth surface, and is easy to handle. The anode may be made of transparent high-conductivity metal such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin dioxide (SnO)2) Zinc oxide (ZnO), etc., ITO is preferred.
(2) The thickness of the hole transport layer is generally in the range of 5nm to 5 μm, and preferred compounds include phthalocyanine compounds, aromatic amine compounds, and the like, such as 4,4 ' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviated as NPB), N, N ' -bis (3-methylphenyl) -N, N ' -diphenylbiphenyl (TPD); 1,3, 5-tris (3-methylbenzhydrylamino) benzene (m-MTDATA), and the like. NPB is preferred in the present invention.
(3) The organic light-emitting layer of the present invention adopts a method of doping a phosphorescent dye in a host material. The metal aluminum complex provided by the invention is selected as a main material, and simultaneously, the preferable common main materials such as CBP, Bebq and the like are selected for comparison. Preferred phosphorescent dyes are complexes of metallic iridium, the most commonly used being Ir (piq)2acac,Ir(ppy)3FIr6, and the like. According to the invention, different phosphorescent dyes are selected according to corresponding devices, and the doping concentration in the main body is 5-10% of the total mass of the luminescent layer.
(4) The electron transmission layer and the hole blocking layer are made of the metal aluminum complex, and simultaneously, the preferred common electron transmission material and the preferred hole blocking material Alq are selected3TPBI and Bphen, etc.
(5) The cathode can be made of lithium, magnesium, aluminum, calcium, aluminum lithium alloy, magnesium silver alloy, magnesium indium alloy and other low work function metals or alloys or electrode layers formed by alternately forming metal and metal fluoride, and the invention preferably selects Mg, Ag/Ag electrode and LiF/Al electrode.
A series of organic electroluminescent devices of the invention are prepared according to the following method: cleaning a glass substrate with an anode by using a cleaning agent, deionized water, ultraviolet irradiation and the like; vacuum evaporating a hole transport layer; vacuum evaporating a light-emitting layer containing the host material of the present invention and a phosphorescent dye; vacuum evaporation comprises the electron transport layer of the invention; and (5) vacuum evaporating a cathode.
EXAMPLE fifty-nine A comparative device-1 and OLED-1-OLED-20 were prepared
Preparation of comparative device-1: the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding the surface with low-energy cation beam.
Placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form NPB as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating a layer of doped phosphorescent material Ir (piq) on the hole transport layer2acacCBP of (a) as a light emitting layer of the device, CBP and Ir (piq)2The evaporation rate ratio of acac is 10: 1, Ir (piq)2The doping concentration of the acac in the CBP is 10 weight percent (10wt%), the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
a layer of BALq material is vacuum evaporated on the organic light-emitting layer to be used as an electron transport layer of the device, the evaporation rate is 0.2nm/s, and the total evaporation film thickness is 40 nm;
and sequentially performing vacuum evaporation on the electron transport layer to form Mg: an Ag alloy layer and an Ag layer as a cathode of the device, wherein Mg: the evaporation rate of the Ag alloy layer is 2.0-3.0 nm/s, the thickness is 100nm, the evaporation rate of the Ag layer is 0.3nm/s, and the thickness is 100 nm.
OLED-1 to OLED-20 were prepared according to the above method, with the electron transport material changed, the device properties are detailed in Table 1:
TABLE 1
From the above table, it can be seen that the material provided by the present invention can be used as an electron transport material and an electron injection material, the lighting voltage of the device is significantly reduced, and the maximum power efficiency is about twice as high as that of the BAlq material.
Example sixty comparative devices-2 and OLED-21-30 were prepared
Preparation of comparative device-2: devices were prepared according to the above examples, but the materials of the main light-emitting layer, electron transport layer and cathode were varied.
And a layer of mCP doped with a phosphorescent material FIrPic is vacuum evaporated on the hole transport layer to be used as a light emitting layer of the device, and the evaporation rate ratio of the mCP to the FIrPic is 12: 1, the doping concentration of the FIrPic in the mCP is 8 weight percent (8wt%), the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
a TPBi material is evaporated on the organic light-emitting layer in vacuum to serve as an electron transport layer of the device, the evaporation rate is 0.5nm/s, and the total evaporation film thickness is 40 nm;
and sequentially vacuum evaporating a LiF layer and an Al layer on the electron transport layer to serve as a cathode of the device, wherein the evaporation rate of the LiF layer is 0.20-0.30 nm/s, the thickness of the LiF layer is 5nm, the evaporation rate of the Al layer is 5-10nm/s, and the thickness of the Al layer is 150 nm.
The OLED-21-OLED-30 is prepared according to the method, the main material is changed, and the performance of the device is detailed in a table 2:
TABLE 2
As can be seen from the table above, the material provided by the invention is used as a blue phosphorescent host material, the color purity of the device is high, and the power efficiency reaches 26.9 cd/A.
Example sixty one comparative device-3 and OLED-31-40 were prepared
Preparation of comparative device-3: devices were prepared according to the above examples, but the materials of the main light-emitting layer, the electron transport layer, were changed.
Vacuum evaporating a layer of doped phosphorescent material Ir (ppy) on the hole transport layer3The CBP of (1) is used as a light emitting layer of the device, and the CBP and Ir (ppy)3The evaporation rate ratio of (2) is 20: 1, Ir (ppy)3The doping concentration in CBP is 5 weight percent (5wt%), the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
a layer of Bphen is evaporated on the organic light-emitting layer in vacuum to be used as a hole blocking layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 20 nm;
vacuum evaporating a layer of Alq on the hole barrier layer3The material is used as an electron transport layer of a device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 20 nm.
The OLED-31-OLED-40 is prepared according to the method, the hole blocking layer material is changed, and the performance of the device is detailed in a table 3:
TABLE 3
As can be seen from the table, the material provided by the invention is used as a hole blocking layer material, the device has low lighting voltage, and the highest power efficiency reaches 75.3 cd/A.
Example sixty-two comparative devices-4 and OLED-41-42 were prepared
Preparation of comparative device-4: comparative device-4 was prepared according to the above example except that the structure of the main light emitting layer was changed.
Vacuum evaporating a layer containing FIr6 and (fbi) on the hole transport layer2A double doped phosphorescent light emitting layer of Ir (acac), FIir6 having a doping concentration of 10wt% in the host material (fbi)2Ir (acac) was doped in the host material at a concentration of 0.75wt% (0.75wt%), with a total evaporation rate of 0.2nm/s and a total film thickness of 20 nm.
The OLED-41-OLED-42 is prepared according to the method, the material of the main light-emitting layer is changed, and the performance of the device is detailed in a table 4:
TABLE 4
As can be seen from the above table, the material provided by the invention is used as a main material of a double-phosphorescence white light device, the color purity of the device is high, and the external quantum efficiency can reach 20.1%.
Although the present invention has been described in connection with the preferred embodiments, the present invention is not limited to the above-described embodiments and the accompanying drawings, and it is to be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the present invention, and the scope of the present invention is outlined by the appended claims.
Claims (5)
1. A metal aluminum complex, wherein the complex has the formula:
2. the metallic aluminum complex according to claim 1, which is used as a light emitting layer material, an electron transport layer material or a hole blocking layer material in an organic electroluminescent device.
3. An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is a combination of one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and is characterized in that: the light emitting layer material is one or more of the metal aluminum complexes as set forth in claim 1.
4. An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is a combination of one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and is characterized in that: the electron transport layer material is one or more of the metal aluminum complexes as set forth in claim 1.
5. An organic electroluminescent device comprises a first electrode, a second electrode and a plurality of organic functional layers positioned between the two electrodes;
the organic functional layer is a combination of one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and is characterized in that: the hole blocking layer material is one or more of the aluminum metal complexes as set forth in claim 1.
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| US20040214034A1 (en) * | 1997-10-09 | 2004-10-28 | Koji Utsugi | Organic thin-film el device |
| CN1692680A (en) * | 2002-09-20 | 2005-11-02 | 出光兴产株式会社 | Organic electroluminescent element |
| CN1832924A (en) * | 2003-08-07 | 2006-09-13 | 新日铁化学株式会社 | Aluminum chelate complex for organic el material |
| CN101088178A (en) * | 2004-12-30 | 2007-12-12 | E.I.内穆尔杜邦公司 | Organometallic complexes |
| CN102017218A (en) * | 2008-05-08 | 2011-04-13 | 新日铁化学株式会社 | Organic electroluminescent element |
| CN102264864A (en) * | 2008-10-29 | 2011-11-30 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using same |
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| US20040214034A1 (en) * | 1997-10-09 | 2004-10-28 | Koji Utsugi | Organic thin-film el device |
| CN1692680A (en) * | 2002-09-20 | 2005-11-02 | 出光兴产株式会社 | Organic electroluminescent element |
| CN1832924A (en) * | 2003-08-07 | 2006-09-13 | 新日铁化学株式会社 | Aluminum chelate complex for organic el material |
| CN101088178A (en) * | 2004-12-30 | 2007-12-12 | E.I.内穆尔杜邦公司 | Organometallic complexes |
| CN102017218A (en) * | 2008-05-08 | 2011-04-13 | 新日铁化学株式会社 | Organic electroluminescent element |
| CN102264864A (en) * | 2008-10-29 | 2011-11-30 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using same |
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