CN104178106A - Red phosphorescence iridium metal complex, preparation method and organic electroluminescent device - Google Patents
Red phosphorescence iridium metal complex, preparation method and organic electroluminescent device Download PDFInfo
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- CN104178106A CN104178106A CN201310192640.2A CN201310192640A CN104178106A CN 104178106 A CN104178106 A CN 104178106A CN 201310192640 A CN201310192640 A CN 201310192640A CN 104178106 A CN104178106 A CN 104178106A
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- acenaphthene
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 112
- -1 iridium metal complex Chemical class 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 65
- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical compound N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940049706 benzodiazepine Drugs 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 46
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 37
- 238000000746 purification Methods 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000003480 eluent Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 238000010898 silica gel chromatography Methods 0.000 claims description 24
- 238000010025 steaming Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000005401 electroluminescence Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 10
- 230000036571 hydration Effects 0.000 claims description 10
- 238000006703 hydration reaction Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 35
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 abstract description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 8
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000003335 steric effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- 125000005605 benzo group Chemical group 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- GBKOPVNCPCSVDJ-UHFFFAOYSA-N 1-(1,2-dihydroacenaphthylen-5-yl)phthalazine Chemical class C1CC2=CC=C(C3=CC=CC1=C23)C2=NN=CC3=CC=CC=C23 GBKOPVNCPCSVDJ-UHFFFAOYSA-N 0.000 description 8
- VNHBJAAKFVLTMX-UHFFFAOYSA-N 2-(1,2-dihydroacenaphthylen-5-yl)quinoxaline Chemical compound C1Cc2ccc(-c3cnc4ccccc4n3)c3cccc1c23 VNHBJAAKFVLTMX-UHFFFAOYSA-N 0.000 description 8
- ALQPSHPOAMPZGY-UHFFFAOYSA-N 3-(1,2-dihydroacenaphthylen-5-yl)cinnoline Chemical class C1CC2=CC=C(C3=CC=CC1=C23)C4=CC5=CC=CC=C5N=N4 ALQPSHPOAMPZGY-UHFFFAOYSA-N 0.000 description 8
- QGNDNILGHUGVKW-UHFFFAOYSA-N 4-(1,2-dihydroacenaphthylen-5-yl)quinazoline Chemical compound C1CC2=CC=C(C3=CC=CC1=C23)C4=NC=NC5=CC=CC=C54 QGNDNILGHUGVKW-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- UUUVDWHAPWIJBM-UHFFFAOYSA-N 2-(1,2-dihydroacenaphthylen-5-yl)quinazoline Chemical compound C1CC2=CC=C(C3=CC=CC1=C23)C4=NC5=CC=CC=C5C=N4 UUUVDWHAPWIJBM-UHFFFAOYSA-N 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 150000001854 cinnolines Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 229910052754 neon Inorganic materials 0.000 description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 3
- ALHUXMDEZNLFTA-UHFFFAOYSA-N Cc1nc(cccc2)c2nc1 Chemical compound Cc1nc(cccc2)c2nc1 ALHUXMDEZNLFTA-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QQOOBOLYTVPEND-UHFFFAOYSA-N bromobenzene;pyrimidine Chemical compound C1=CN=CN=C1.BrC1=CC=CC=C1 QQOOBOLYTVPEND-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- CEYRROMZZGLFSL-UHFFFAOYSA-N Cc1cc(cccc2)c2nn1 Chemical compound Cc1cc(cccc2)c2nn1 CEYRROMZZGLFSL-UHFFFAOYSA-N 0.000 description 1
- DXPQTHAFYUTZRR-UHFFFAOYSA-N Cc1nc2ccccc2cn1 Chemical compound Cc1nc2ccccc2cn1 DXPQTHAFYUTZRR-UHFFFAOYSA-N 0.000 description 1
- VXDPPGNAYZJZPM-UHFFFAOYSA-N Cc1nncc2ccccc12 Chemical compound Cc1nncc2ccccc12 VXDPPGNAYZJZPM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical class [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a red phosphorescence iridium metal complex, its preparation method and an organic electroluminescent device. The structural formula of the red phosphorescence iridium metal complex is as defined in the specification, wherein -Ar is as defined in the specification. According to the above red phosphorescence iridium metal complex, acenaphthene-5-yl is introduced to a benzodiazepine hexatomic ring to obtain satisfactory red emission wavelength, and a space steric effect is generated to some extent. Thus, iridium interatomic direct action is minimized, self-quenching of triplet excitons is reduced, and there is intense phosphorescence emission at room temperature. Meanwhile, the acenaphthenyl group and the benzodiazepine hexatomic ring structure which have high planar rigidity are beneficial to phosphorescence luminescence on one hand. On the other hand, highest occupied molecular orbital (HOMO) energy level and lowest unoccupied molecular orbital (LUMO) energy level of the material can be controlled effectively. In addition, it is beneficial to balance charge transfer in the device. If the red phosphorescence iridium metal complex is applied to the organic electroluminescent device, electroluminescent performance of the device can be raised.
Description
Technical field
The present invention relates to electroluminescent material technical field, particularly relate to a kind of red phosphorescent iridium metal complex, its preparation method and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, make low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
In order to make organic electroluminescence device obtain full-color demonstration, generally must obtain ruddiness phosphorescence, green glow phosphorescence and the blue emitting phosphor material of excellent performance simultaneously.Generally speaking, the development of blue emitting phosphor material always lags behind ruddiness and green glow, and with regard to single, from this index of purity of color, blue emitting phosphor material seldom can be accomplished the purity of color of the dark red light of picture and dark green light so far.In order to produce gratifying white light organic electroluminescent device, that select at present or taking the phosphor material of sky blue light as main, as two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), and it is just passable that this just requires arranged in pairs or groups ruddiness phosphor material will be connected to saturated red scarlet.So the ruddiness phosphorescent light-emitting materials of developing high color purity is still a large focus of organic electroluminescent research field.But the efficiency ratio of current ruddiness phosphorescent light-emitting materials is lower, is applied in electroluminescent device, be difficult to obtain satisfied luminescent properties.
Summary of the invention
Based on this, be necessary to provide a kind of red phosphorescent iridium metal complex of the luminescent properties that can improve electroluminescent device.
A kind of preparation method of red phosphorescent iridium metal complex further, is provided.
A kind of organic electroluminescence device that uses this red phosphorescent iridium metal complex is also provided.
A kind of red phosphorescent iridium metal complex, structural formula is as follows:
Wherein ,-Ar is
A preparation method for red phosphorescent iridium metal complex, comprises the steps:
In the first atmosphere of inert gases, for 4:4.5～5, Ar-Br and acenaphthene-5-boric acid are dissolved in the first solvent in molar ratio, add catalyzer and carbonate solution, carry out Suzuki linked reaction 8～12 hours, after separation and purification, obtain encircling master metal part acenaphthene-5-base benzodiazepine six-ring, wherein, described Ar is
In the second atmosphere of inert gases, be that 2.2～3:1 is dissolved in described ring master metal part acenaphthene-5-base benzodiazepine six-ring and three hydration iridous chlorides in the second solvent in molar ratio, be heated to reflux state reaction 22～25 hours, after separation and purification, obtain chlorine bridge dipolymer;
In the 3rd atmosphere of inert gases, 0.5:1.2～2 are dissolved in described chlorine bridge dipolymer and methyl ethyl diketone in the 3rd solvent in molar ratio, add carbonate, be heated to reflux state reaction 8～15 hours, after separation and purification, obtain red phosphorescent iridium metal complex, the structural formula of described red phosphorescent iridium metal complex is:
In an embodiment, described the first solvent is toluene or tetrahydrofuran (THF) therein; Described the second solvent is 2-methyl cellosolve or cellosolvo; Described the 3rd solvent is 2-methyl cellosolve, cellosolvo or methylene dichloride.
In an embodiment, described catalyzer is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium therein.
In an embodiment, the mol ratio of described catalyzer and described acenaphthene-5-boric acid is 0.2～0.24:4.5～5 therein.
Therein in an embodiment, after separation and purification, obtain encircling in the step of master metal part acenaphthene-5-base benzodiazepine six-ring, the method of separation and purification is specially: after reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:3～1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure ring master metal part acenaphthene-5-base benzodiazepine six-ring.
Therein in an embodiment, after separation and purification, obtain in the step of chlorine bridge dipolymer, the method of separation and purification is specially: reaction finishes, and reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes, and crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:4～1:6 and the mixed solution of normal hexane are eluent, obtain pure chlorine bridge dipolymer.
In an embodiment, obtain in the step of red phosphorescent iridium metal complex after separation and purification therein, the method for separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, by chloroform and distilled water extracted several times.Organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized, crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:4～1:10 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, the dry rear final pure red phosphorescence iridium metal complex that obtains.
A kind of organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electronic injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises luminous material of main part and be doped in the luminous guest materials in described luminous material of main part, and described luminous guest materials is above-mentioned red phosphorescent iridium metal complex.
Above-mentioned red phosphorescent iridium metal complex is taking acenaphthene-5-base benzodiazepine six-ring as cyclic metal complexes agent structure, taking methyl ethyl diketone as assistant ligand, acenaphthene-5-base is incorporated in benzodiazepine six-ring and can obtains and be satisfied with red light-emitting wavelength, and produce to a certain extent space steric effect, thereby the direct effect between minimizing iridium atom, the self-quenching phenomenon that reduces triplet exciton, at room temperature just has very strong phosphorescent emissions; Simultaneously, the acenaphthenyl and the benzodiazepine six-membered ring structure that have respectively larger planar rigidity are conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, be applied in organic electroluminescence device, can improve the electroluminescent properties of device.
Brief description of the drawings
Fig. 1 is the preparation method's of the red phosphorescent iridium metal complex of an embodiment schema;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, C prepared by embodiment 1
2'] (methyl ethyl diketone) close the utilizing emitted light spectrogram of complex of iridium.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
A kind of red phosphorescent iridium metal complex, its structural formula is as follows:
Wherein ,-Ar is phthalazinyl, cinnolines base, benzo pyrimidyl or quinoxalinyl.
The structural formula of phthalocyanine base is as follows:
In the time that-Ar is phthalazinyl, the 3-position C of phthalazinyl is connected with the 5-position C of the acenaphthenyl in red phosphorescent iridium metal complex, and the structural formula of red phosphorescent iridium metal complex is as follows:
The structural formula of cinnolines base is as follows:
In the time that-Ar is cinnolines base, the 3-position C of cinnolines base is connected with the 5-position C of the acenaphthenyl in red phosphorescent iridium metal complex, and the structural formula of red phosphorescent iridium metal complex is as follows:
The structural formula of benzo pyrimidyl is as follows:
In the time that-Ar is benzo pyrimidyl, the 2-position C of benzo pyrimidyl is connected with the 5-position C of the acenaphthenyl in red phosphorescent iridium metal complex, and the structural formula of red phosphorescent iridium metal complex is as follows:
In another embodiment, in the time that-Ar is benzo pyrimidyl, the 4-position C of benzo pyrimidyl is connected with the 5-position C of the acenaphthenyl in red phosphorescent iridium metal complex, and the structural formula of red phosphorescent iridium metal complex is as follows:
The structural formula of quinoxalinyl is as follows:
In the time that-Ar is quinoxalinyl, the 2-position C of quinoxalinyl is connected with the 5-position C of the acenaphthenyl in red phosphorescent iridium metal complex, and the structural formula of red phosphorescent iridium metal complex is as follows:
Above-mentioned red phosphorescent iridium metal complex is taking acenaphthene-5-base benzodiazepine six-ring as cyclic metal complexes agent structure, taking methyl ethyl diketone as assistant ligand, acenaphthene-5-base is incorporated in benzodiazepine six-ring (as phthalazines, cinnolines, benzo pyrimidine or quinoxaline), acenaphthenyl can be realized the adjusting to material glow color from the chemical modification method of different benzodiazepine six-membered ring structure coupling, thereby obtain the phosphorescent emissions of different red emission wavelengths, obtain satisfied ruddiness.
And, the iridium metal complex that acenaphthene-5-base benzodiazepine six-ring main body and acetyl acetone ligands form produces space steric effect to a certain extent, thereby the direct effect between minimizing iridium atom, the self-quenching phenomenon of minimizing triplet exciton, at room temperature just has very strong phosphorescent emissions; Simultaneously, the acenaphthenyl and the benzodiazepine six-membered ring structure that have respectively larger planar rigidity are conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, be applied in organic electroluminescence device, can improve the electroluminescent properties of device.
Refer to Fig. 1, the preparation method of the red phosphorescent iridium metal complex of an embodiment, comprises the steps:
Step S110: in the first atmosphere of inert gases, for 4:4.5～5, Ar-Br and acenaphthene-5-boric acid are dissolved in the first solvent in molar ratio, add catalyzer and carbonate solution, carry out Suzuki linked reaction 8～12 hours, after separation and purification, obtain encircling master metal part acenaphthene-5-base benzodiazepine six-ring.
The first rare gas element is argon gas, helium or neon.
The first solvent is toluene or tetrahydrofuran (THF).The consumption of the first solvent is so that Ar-Br and acenaphthene-5-boric acid are fully dissolved as suitable.Catalyzer is palladium catalyst, is preferably tetra-triphenylphosphine palladium (Pd (pph
3)
4) or dichloro bi triphenyl phosphine palladium (Pd (PPh
3)
2cl
2).
Preferably, the mol ratio of catalyzer and acenaphthene-5-boric acid is 0.2～0.24:4.5～5.
Carbonate solution is sodium carbonate or solution of potassium carbonate.The volumetric molar concentration of carbonate solution is 0.8mmol/mL.Carbonate in carbonate solution and the mol ratio of catalyzer are 8:0.2.
For 4:4.5～5, Ar-Br and acenaphthene-5-boric acid are dissolved in the first solvent in molar ratio, add catalyzer and carbonate solution, heating is stirred 8～12 hours under reflux state, carry out Suzuki linked reaction, after separation and purification, obtain encircling master metal part acenaphthene-5-base benzodiazepine six-ring.
Wherein, Ar is phthalazines, cinnolines, benzo pyrimidine or quinoxaline, and the structure of Ar-Br is
The reaction formula of above-mentioned Suzuki linked reaction is:
The method of separation and purification is specially: after reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:3～1:5 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, and after being dried, obtain pure ring master metal part acenaphthene-5-base benzodiazepine six-ring.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Step S120: in the second atmosphere of inert gases, be that 2.2～3:1 is dissolved in ring master metal part acenaphthene-5-base benzodiazepine six-ring and three hydration iridous chlorides in the second solvent in molar ratio, be heated to reflux state reaction 22～25 hours, after separation and purification, obtain chlorine bridge dipolymer.
The second rare gas element is argon gas, helium or neon.
The second solvent is 2-methyl cellosolve or cellosolvo.The consumption of the second solvent is so that ring master metal part acenaphthene-5-base benzodiazepine six-ring and three hydration iridous chlorides are fully dissolved as suitable.
Be that 2.2～3:1 will encircle master metal part acenaphthene-5-base benzodiazepine six-ring and three hydration iridous chloride (IrCl in molar ratio
33H
2o) be dissolved in the second solvent, be heated to reflux state reaction 22～25 hours, obtain chlorine bridge dipolymer after separation and purification, reaction formula is as follows:
The method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes, and crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:4～1:6 and the mixed solution of normal hexane are eluent, obtain pure chlorine bridge dipolymer.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Step S130: in the 3rd atmosphere of inert gases, 0.5:1.2～2 are dissolved in chlorine bridge dipolymer and methyl ethyl diketone in the 3rd solvent in molar ratio, add carbonate, be heated to reflux state reaction 8～15 hours, after separation and purification, obtain red phosphorescent iridium metal complex.
The 3rd rare gas element is argon gas, helium or neon.
The 3rd solvent is 2-methyl cellosolve, cellosolvo or methylene dichloride.The consumption of the 3rd solvent is so that chlorine bridge dipolymer and methyl ethyl diketone are fully dissolved as suitable.
Carbonate is sodium carbonate or salt of wormwood.
0.5:1.2～2 are dissolved in chlorine bridge dipolymer and methyl ethyl diketone in the 3rd solvent in molar ratio, add carbonate, be heated to reflux state reaction 8～15 hours, chlorine bridge dipolymer and assistant ligand source methyl ethyl diketone generation ligand exchange, after separation and purification, obtain red phosphorescent iridium metal complex, reaction formula is as follows:
The structural formula of the red phosphorescent iridium metal complex preparing is
Wherein ,-Ar is
The method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized, crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:4～1:10 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, the dry rear final pure red phosphorescence iridium metal complex that obtains.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Preparation method's reaction conditions gentleness of above-mentioned red phosphorescent iridium metal complex, lower to equipment requirements, preparation cost is low, is easy to extensive preparation.
Refer to Fig. 2, the organic electroluminescence device 300 of one embodiment, comprises the substrate 301, anode 302, hole injection layer 303, hole transmission layer 304, luminescent layer 305, hole blocking layer 306, electron transfer layer 307, electronic injection buffer layer 308 and the negative electrode 309 that stack gradually.
The material of substrate 301, anode 302, hole injection layer 303, hole transmission layer 304, hole blocking layer 306, electron transfer layer 307, electronic injection buffer layer 308 and negative electrode 309 is respectively the common used material of this area.For example, substrate 101 is glass substrate, the material of anode 302 is that the material of tin indium oxide (ITO), hole injection layer 303 is 4,4', the material of 4''-tri-(N-(naphthalene-2-yl)-N-phenyl amino) triphenylamine (2-TNATA), hole transmission layer 304 is N, two (1-the naphthyl)-N of N'-, the material of N '-phenylbenzene benzidine (NPB), hole blocking layer 306 is 2,9-dimethyl-4, the material of 7-phenylbenzene-phenanthrolene (BCP), electron transfer layer 307 is three (oxine) aluminium (Alq
3), the material of electronic injection buffer layer 308 is that the material of oxine lithium (Liq), negative electrode 309 is metallic aluminium (Al).
The material of luminescent layer 305 comprises luminous material of main part and is doped in the luminous guest materials in luminous material of main part.Wherein, luminous guest materials is above-mentioned red phosphorescent iridium metal complex, and luminous material of main part is N, two carbazyl-4 of N'-, 4'-dipyridyl (CBP).The mass percent that above-mentioned red phosphorescent iridium metal complex accounts for luminous material of main part is 8%.
Above-mentioned red phosphorescent iridium metal complex and luminous material of main part have good consistency, can be widely used in and prepare ruddiness or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device 300 is due to the red phosphorescent iridium metal complex that contains high color purity in luminescent layer 305, thereby can launch high purity ruddiness, and this red phosphorescent iridium metal complex is conducive to the electric charge transmission in balancing device, can improve the electroluminescent properties of organic electroluminescence device 300.
It is below specific embodiment.
Embodiment 1
Red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, C
2'] (methyl ethyl diketone) close the synthetic of complex of iridium.
Red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, C
2'] (methyl ethyl diketone) to close the structural formula of complex of iridium as follows:
(1) 1-(acenaphthene-5-yl) phthalazines is synthetic
In argon atmosphere, 0.84g (4mmol) 1-bromine phthalazines, 0.95g (4.8mmol) acenaphthene-5-boric acid and 0.23g (0.20mmol) tetra-triphenylphosphine palladium are dissolved in 30mL toluene, in reaction system, drip the aqueous solution of 10mL containing 0.85g (8mmol) sodium carbonate subsequently, heating, stirs and carries out Suzuki linked reaction 10h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, with suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:3 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 1-(acenaphthene-5-yl) phthalazines 0.74g, yield is 65.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C20H14N2
Theoretical value: C, 85.08; H, 5.00; N, 9.92;
Measured value: C, 85.14; H, 5.02; N, 9.84.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(acenaphthene-5-yl) phthalazines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 1-(acenaphthene-5-yl) phthalazines
In argon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.70g (2.5mmol) 1-(acenaphthene-5-yl) phthalazines are dissolved in 20mL2-ethoxy ethanol, be heated to reflux state reaction 24h.Reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:5 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer 0.27g, yield is 34.2%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1580.3 (M
+)
Ultimate analysis: C80H52Cl2Ir2N8
Theoretical value: C, 60.79; H, 3.32; Cl, 4.49; Ir, 24.32; N, 7.09;
Measured value: C, 60.74; H, 3.38; Cl, 4.43; Ir, 24.35; N, 7.10.
The material that the above-mentioned reaction of above data acknowledgement obtains be main part be 1-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-(acenaphthene-5-yl) phthalazines-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of complex of iridium
In argon atmosphere, be being dissolved in the 20mL2-ethoxy ethanol solvent of degasification containing iridium dichloro dipolymer, 0.15g (1.5mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate of 1-(acenaphthene-5-yl) phthalazines by the main part of 0.79g (0.5mmol), be heated to reflux state reaction 10h.After reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [1-(acenaphthene-5-yl) phthalazines-N, the C of obtaining after dry
2'] (methyl ethyl diketone) close complex of iridium 0.44g, yield is 51.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.23; H, 3.97; Ir, 22.55; N, 6.53; O, 3.72.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [1-(acenaphthene-5-yl) phthalazines-N, C of red phosphorescent
2'] (methyl ethyl diketone) close complex of iridium.
Fig. 3 is two [1-(acenaphthene-5-yl) phthalazines-N, C of above-mentioned red phosphorescent
2'] (methyl ethyl diketone) close the utilizing emitted light spectrogram of complex of iridium.As shown in Figure 3, transverse axis is emission wavelength (nm of unit), and the longitudinal axis is the photoluminescence intensity (a.u.) after normalization method, red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, C
2'] (methyl ethyl diketone) close complex of iridium CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 627nm place, can be used as ruddiness electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ ph=0.40), records the Φ PL=0.25 of end product, red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, the C of visible the present embodiment
2'] (methyl ethyl diketone) close complex of iridium and have higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2
Red phosphorescent two [3-(acenaphthene-5-yl) cinnolines-N, C
2'] (methyl ethyl diketone) close the synthetic of complex of iridium.
It is as follows that red phosphorescent two [3-(acenaphthene-5-yl) cinnolines-N, C2'] (methyl ethyl diketones) closes the structural formula of complex of iridium:
(1) 3-(acenaphthene-5-yl) cinnolines is synthetic
In helium atmosphere, 0.84g (4mmol) 3-bromine cinnolines, 0.99g (5mmol) acenaphthene-5-boric acid and 0.28g (0.24mmol) tetra-triphenylphosphine palladium are dissolved in 25mL tetrahydrofuran (THF), in reaction system, drip the aqueous solution of 10mL containing 1.38g (10mmol) salt of wormwood subsequently.Heating, stirs and carries out Suzuki linked reaction 12h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, with suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed except the solvent in filtrate.Oily crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:3 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, and after being dried, obtains pure 3-(acenaphthene-5-yl) cinnolines 0.76g, and yield is 67.3%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C20H14N2
Theoretical value: C, 85.08; H, 5.00; N, 9.92;
Measured value: C, 85.14; H, 5.02; N, 9.84.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(acenaphthene-5-yl) cinnolines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 3-(acenaphthene-5-yl) cinnolines
In helium atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 1.13g (3mmol) 3-(acenaphthene-5-yl) cinnolines are dissolved in 20mL2-methyl cellosolve, be heated to reflux state reaction 22h.Reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:4 and the mixed solution of normal hexane are eluent, obtain pure main part and be 3-(acenaphthene-5-yl) cinnolines containing iridium dichloro dipolymer 0.28g, yield is 35.4%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1580.3 (M
+)
Ultimate analysis: C80H52Cl2Ir2N8
Theoretical value: C, 60.79; H, 3.32; Cl, 4.49; Ir, 24.32; N, 7.09;
Measured value: C, 60.75; H, 3.38; Cl, 4.43; Ir, 24.39; N, 7.05.
The material that the above-mentioned reaction of above data acknowledgement obtains be main part be 3-(acenaphthene-5-yl) cinnolines containing iridium dichloro dipolymer.
(3) two [3-(acenaphthene-5-yl) cinnolines-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of complex of iridium
In helium atmosphere, be being dissolved in the 20mL dichloromethane solvent of degasification containing iridium dichloro dipolymer, 0.20g (2mmol) methyl ethyl diketone and 0.69g (5mmol) salt of wormwood of 3-(acenaphthene-5-yl) cinnolines by the main part of 0.79g (0.5mmol), be heated to reflux state reaction 15h.After reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized.Crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, dry rear final pure red phosphorescence two [3-(acenaphthene-5-yl) cinnolines-N, the C of obtaining
2'] (methyl ethyl diketone) close complex of iridium 0.45g, yield is 52.7%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M
+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.25; H, 3.95; Ir, 22.54; N, 6.50; O, 3.76.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [3-(acenaphthene-5-yl) cinnolines-N, C of red phosphorescent
2'] (methyl ethyl diketone) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 636nm place.In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.35.
Embodiment 3
Red phosphorescent two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (methyl ethyl diketone) close the synthetic of complex of iridium.
Red phosphorescent two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (methyl ethyl diketone) to close the structural formula of complex of iridium as follows:
(1) 2-(acenaphthene-5-yl) benzo pyrimidine is synthetic
In argon atmosphere, 0.83g (4mmol) 2-bromobenzene pyrimidine, 0.99g (5mmol) acenaphthene-5-boric acid and 0.17g (0.24mmol) dichloro bi triphenyl phosphine palladium are dissolved in 20mL toluene, in reaction system, drip the aqueous solution of 10mL containing 1.06g (10mmol) sodium carbonate subsequently, heating, stirring reaction 8h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times.Organic phase anhydrous magnesium sulfate drying, filters.Rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 2-(acenaphthene-5-yl) benzo pyrimidine 0.56g, yield is 49.6%.Concrete reaction formula is as follows:
(2) main part is the synthesizing containing iridium dichloro dipolymer of 2-(acenaphthene-5-yl) benzo pyrimidine
In argon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.85g (3mmol) 2-(acenaphthene-5-yl) benzo pyrimidine are dissolved in 25mL2-ethoxy ethanol, be heated to reflux state reaction 25h.Reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:5 and the mixed solution of normal hexane are eluent, obtain pure main part and be 2-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer 0.26g, yield is 32.9%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1580.3 (M
+)
Ultimate analysis: C80H52Cl2Ir2N8
Theoretical value: C, 60.79; H, 3.32; Cl, 4.49; Ir, 24.32; N, 7.09;
Measured value: C, 60.73; H, 3.39; Cl, 4.53; Ir, 24.30; N, 7.05.
The material that the above-mentioned reaction of above data acknowledgement obtains be main part be 2-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer.
(3) two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of complex of iridium
In argon atmosphere, be being dissolved in the 25mL2-ethoxy ethanol solvent of degasification containing iridium dichloro dipolymer, 0.15g (1.5mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate of 2-(acenaphthene-5-yl) benzo pyrimidine by the main part of 0.79g (0.5mmol), be heated to reflux state reaction 8h.After reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:4 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [2-(acenaphthene-5-yl) benzo pyrimidine-N, the C of obtaining after dry
2'] (methyl ethyl diketone) close complex of iridium 0.39g, yield is 45.7%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.18; H, 3.95; Ir, 22.58; N, 6.52; O, 3.77.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (methyl ethyl diketone) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 628nm place.In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ ph=0.40), records the Φ PL=0.29 of end product.
Embodiment 4
Red phosphorescent two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (methyl ethyl diketone) close the synthetic of complex of iridium.
Red phosphorescent two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (methyl ethyl diketone) to close the structural formula of complex of iridium as follows:
(1) 4-(acenaphthene-5-yl) benzo pyrimidine is synthetic
In argon atmosphere, 0.83g (4mmol) 4-bromobenzene pyrimidine, 0.99g (5mmol) acenaphthene-5-boric acid and 0.28g (0.24mmol) tetra-triphenylphosphine palladium are dissolved in 20mL tetrahydrofuran (THF), in reaction system, drip the aqueous solution of 10mL containing 1.38g (10mmol) salt of wormwood subsequently.Heating, stirring reaction 10h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times.Organic phase anhydrous magnesium sulfate drying, filters.Rotation is steamed except the solvent in filtrate.Oily crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:5 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, and after being dried, obtains pure 4-(acenaphthene-5-yl) benzo pyrimidine 0.57g, and yield is 50.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C20H14N2
Theoretical value: C, 85.08; H, 5.00; N, 9.92;
Measured value: C, 85.15; H, 4.90; N, 9.95.
The material that the above-mentioned reaction of above data acknowledgement obtains is 4-(acenaphthene-5-yl) benzo pyrimidine.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 4-(acenaphthene-5-yl) benzo pyrimidine
In argon atmosphere, 0.35g (1mmol) three hydration iridous chlorides, 0.70g (2.5mmol) 4-(acenaphthene-5-yl) benzo pyrimidine are dissolved in 25mL2-methyl cellosolve, be heated to reflux state reaction 24h.Reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:6 and the mixed solution of normal hexane are eluent, obtain pure main part and be 4-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer 0.27g, yield is 34.2%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1580.3 (M
+)
Ultimate analysis: C80H52Cl2Ir2N8
Theoretical value: C, 60.79; H, 3.32; Cl, 4.49; Ir, 24.32; N, 7.09;
Measured value: C, 60.84; H, 3.26; Cl, 4.54; Ir, 24.24; N, 7.12.
The material that the above-mentioned reaction of above data acknowledgement obtains be main part be 4-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer.
(3) two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of complex of iridium
In argon atmosphere, be being dissolved in the 25mL2-methyl cellosolve solvent of degasification containing iridium dichloro dipolymer, 0.20g (2mmol) methyl ethyl diketone and 0.69g (5mmol) salt of wormwood of 4-(acenaphthene-5-yl) benzo pyrimidine by the main part of 0.79g (0.5mmol), be heated to reflux state reaction 10h.After reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:6 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [4-(acenaphthene-5-yl) benzo pyrimidine-N, the C of obtaining after dry
2'] (methyl ethyl diketone) close complex of iridium 0.41g, yield is 48.0%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.26; H, 3.95; Ir, 22.44; N, 6.63; O, 3.72.
The material that the above-mentioned reaction of above data acknowledgement obtains closes iridium for two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C2'] (methyl ethyl diketone).
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 626nm place.In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ ph=0.40), records the Φ PL=0.31 of end product.
Embodiment 5
Red phosphorescent two [2-(acenaphthene-5-yl) quinoxaline-N, C
2'] (methyl ethyl diketone) close the synthetic of complex of iridium.
Red phosphorescent two [2-(acenaphthene-5-yl) quinoxaline-N, C
2'] (methyl ethyl diketone) to close the structural formula of complex of iridium as follows:
(1) 2-(acenaphthene-5-yl) quinoxaline is synthetic
In neon atmosphere, 0.83g (4mmol) 2-bromine quinoxaline, 0.89g (4.5mmol) acenaphthene-5-boric acid and 0.14g (0.20mmol) dichloro bi triphenyl phosphine palladium are dissolved in 20mL toluene, in reaction system, drip the aqueous solution of 10mL containing 1.06g (10mmol) sodium carbonate subsequently.Heating, stirring reaction 10h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times.Organic phase anhydrous magnesium sulfate drying, filters.Rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:4 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 2-(acenaphthene-5-yl) quinoxaline 0.57g, yield is 50.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C20H14N2
Theoretical value: C, 85.08; H, 5.00; N, 9.92;
Measured value: C, 85.14; H, 4.92; N, 9.94.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(acenaphthene-5-yl) quinoxaline.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 2-(acenaphthene-5-yl) quinoxaline
In neon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.62g (2.2mmol) 2-(acenaphthene-5-yl) quinoxaline are dissolved in 25mL2-ethoxy ethanol, be heated to reflux state reaction 24h.Reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction mixture, organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, acetone taking volume ratio as 1:5 and the mixed solution of normal hexane are eluent, obtain pure main part and be 2-(acenaphthene-5-yl) quinoxaline containing iridium dichloro dipolymer 0.32g, yield is 40.6%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1580.3 (M
+)
Ultimate analysis: C80H52Cl2Ir2N8
Theoretical value: C, 60.79; H, 3.32; Cl, 4.49; Ir, 24.32; N, 7.09;
Measured value: C, 60.82; H, 3.35; Cl, 4.41; Ir, 24.35; N, 7.07.
The material that the above-mentioned reaction of above data acknowledgement obtains be main part be 2-(acenaphthene-5-yl) quinoxaline containing iridium dichloro dipolymer.
(3) two [2-(acenaphthene-5-yl) quinoxaline-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of complex of iridium
In neon atmosphere, be being dissolved in the 25mL2-ethoxy ethanol solvent of degasification containing iridium dichloro dipolymer, 0.12g (1.2mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate of 2-(acenaphthene-5-yl) quinoxaline by the main part of 0.79g (0.5mmol), be heated to reflux state reaction 15h.After reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, the methylene dichloride taking volume ratio as 1:4 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [2-(acenaphthene-5-yl) quinoxaline-N, the C of obtaining after dry
2'] (methyl ethyl diketone) close complex of iridium 0.34g, yield is 39.8%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M
+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.20; H, 3.98; Ir, 22.58; N, 6.51; O, 3.73.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [2-(acenaphthene-5-yl) quinoxaline-N, C of red phosphorescent
2'] (methyl ethyl diketone) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 631nm place.In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.23.
Embodiment 6
A kind of organic electroluminescence device, comprises the substrate, anode, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electronic injection buffer layer and the negative electrode that stack gradually.
Wherein, substrate is glass substrate, on a glass-based plate, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as anode, on anode, preparing successively thickness by vacuum evaporation is 4 of 40nm, 4', 4''-tri-(N-(naphthalene-2-yl)-N-phenyl amino) triphenylamine (2-TNATA) layer is as hole injection layer, thickness is the N of 20nm, two (1-the naphthyl)-N of N'-, the luminescent layer that N '-phenylbenzene benzidine (NPB) layer is 30nm as hole transmission layer and thickness, the material of luminescent layer is to comprise luminous material of main part and be doped in the luminous guest materials in luminous material of main part, luminous guest materials is two [1-(acenaphthene-5-yl) phthalazines-N of red phosphorescent prepared by embodiment 1, C
2'] (methyl ethyl diketone) close complex of iridium, luminous material of main part is N, two carbazyl-4 of N'-, and the dopant material forming in 4'-dipyridyl (CBP), the mass percent that luminous guest materials accounts for luminous material of main part is 8%.On this luminescent layer, vacuum evaporation thickness is 10nm 2 successively again, 9-dimethyl-4, three (oxine) aluminium (Alq that 7-phenylbenzene-phenanthrolene (BCP) layer is 20nm as hole blocking layer, thickness
3) oxine lithium (Liq) layer that is 2nm as electron transfer layer, thickness is as electronic injection buffer layer, finally on electronic injection buffer layer, adopt the metal Al layer that vacuum plating techniques of deposition thickness is 100nm, as the negative electrode of organic electroluminescence device, obtain organic electroluminescence device, representation is ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq
3(20nm)/Liq (2nm)/Al (100nm).
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency that records organic electroluminescence device is 6.8%, and maximum lumen efficiency is 5.9lm/W.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a red phosphorescent iridium metal complex, is characterized in that, structural formula is as follows:
Wherein ,-Ar is
2. a preparation method for red phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In the first atmosphere of inert gases, for 4:4.5～5, Ar-Br and acenaphthene-5-boric acid are dissolved in the first solvent in molar ratio, add catalyzer and carbonate solution, carry out Suzuki linked reaction 8～12 hours, after separation and purification, obtain encircling master metal part acenaphthene-5-base benzodiazepine six-ring, wherein, described-Ar is
In the second atmosphere of inert gases, be that 2.2～3:1 is dissolved in described ring master metal part acenaphthene-5-base benzodiazepine six-ring and three hydration iridous chlorides in the second solvent in molar ratio, be heated to reflux state reaction 22～25 hours,, after separation and purification, obtain chlorine bridge dipolymer;
In the 3rd atmosphere of inert gases, 0.5:1.2～2 are dissolved in described chlorine bridge dipolymer and methyl ethyl diketone in the 3rd solvent in molar ratio, add carbonate, be heated to reflux state reaction 8～15 hours, after separation and purification, obtain red phosphorescent iridium metal complex, the structural formula of described red phosphorescent iridium metal complex is:
3. the preparation method of red phosphorescent iridium metal complex according to claim 2, is characterized in that, described the first solvent is toluene or tetrahydrofuran (THF); Described the second solvent is 2-methyl cellosolve or cellosolvo; Described the 3rd solvent is 2-methyl cellosolve, cellosolvo or methylene dichloride.
4. the preparation method of red phosphorescent iridium metal complex according to claim 2, is characterized in that, described catalyzer is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium.
5. the preparation method of red phosphorescent iridium metal complex according to claim 2, is characterized in that, the mol ratio of described catalyzer and described acenaphthene-5-boric acid is 0.2～0.24:4.5～5.
6. the preparation method of red phosphorescent iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain encircling in the step of master metal part acenaphthene-5-base benzodiazepine six-ring, the method of separation and purification is specially: after reacting completely, reaction solution is chilled to room temperature naturally, by suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:3～1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure ring master metal part acenaphthene-5-base benzodiazepine six-ring.
7. the preparation method of red phosphorescent iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain in the step of chlorine bridge dipolymer, the method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes, crude product is carried out to silica gel column chromatography separating-purifying, and the acetone taking volume ratio as 1:4～1:6 and the mixed solution of normal hexane are eluent, obtain pure chlorine bridge dipolymer.
8. the preparation method of red phosphorescent iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain in the step of red phosphorescent iridium metal complex, the method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, methylene dichloride taking volume ratio as 1:4～1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, the dry rear final pure red phosphorescence iridium metal complex that obtains.
9. an organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electronic injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises luminous material of main part and be doped in the luminous guest materials in described luminous material of main part, and described luminous guest materials is red phosphorescent iridium metal complex claimed in claim 1.
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