CN104177436A - Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device - Google Patents
Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device Download PDFInfo
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- 0 CC(c1c2cccc1)=*=CN=C2BrC Chemical compound CC(c1c2cccc1)=*=CN=C2BrC 0.000 description 5
- WUHZFPUXGCAMCJ-UHFFFAOYSA-N Bc1cc2ccccc2[nH]1 Chemical compound Bc1cc2ccccc2[nH]1 WUHZFPUXGCAMCJ-UHFFFAOYSA-N 0.000 description 1
- VERQLIMWPUEIMM-UHFFFAOYSA-N C=[Br]c1nc(cccc2)c2cn1 Chemical compound C=[Br]c1nc(cccc2)c2cn1 VERQLIMWPUEIMM-UHFFFAOYSA-N 0.000 description 1
- HULOCJAWRQUAPG-UHFFFAOYSA-N C=[Br]c1nc(cccc2)c2nc1 Chemical compound C=[Br]c1nc(cccc2)c2nc1 HULOCJAWRQUAPG-UHFFFAOYSA-N 0.000 description 1
- CEYRROMZZGLFSL-UHFFFAOYSA-N Cc1cc(cccc2)c2nn1 Chemical compound Cc1cc(cccc2)c2nn1 CEYRROMZZGLFSL-UHFFFAOYSA-N 0.000 description 1
- ALHUXMDEZNLFTA-UHFFFAOYSA-N Cc1nc(cccc2)c2nc1 Chemical compound Cc1nc(cccc2)c2nc1 ALHUXMDEZNLFTA-UHFFFAOYSA-N 0.000 description 1
- VXDPPGNAYZJZPM-UHFFFAOYSA-N Cc1nncc2ccccc12 Chemical compound Cc1nncc2ccccc12 VXDPPGNAYZJZPM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to red phosphorescence iridium complexes, a preparing method thereof and an organic electroluminescence device. The structure formula of the red phosphorescence iridium complexes is shown in the specification, wherein -Ar is shown in the specification. The red phosphorescence iridium complexes introduce 5-acenaphthenyl into a benzodinitrogen six-membered ring, can obtain a satisfied red light emitting wavelength, and generate steric-hindrance effects to a certain degree, thus reducing direct functions of iridium atoms, reducing self-quenching phenomena of triplet excitons and having strong phosphorescence emission at room temperature. In addition, the red phosphorescence iridium complexes are respectively provided with acenaphthenyl and a benzodinitrogen six-membered ring structure that are high in planar rigidity, thus facilitating phosphorescence luminescence on the one hand, effectively controlling the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of the materials on the other hand, and facilitating charge transfer in balancing devices. Electroluminescence properties of the organic electroluminescence device can be improved by applying the complexes into the organic electroluminescence device.
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-Br 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 by described chlorine bridge dipolymer and 2 in molar ratio, 2,6,6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, add carbonate, be heated to reflux state reaction 8～15 hours, obtain red phosphorescent iridium metal complex after separation and purification, the structural formula of described red phosphorescent iridium metal complex is:
Wherein ,-Ar 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.
Therein in an embodiment, 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, 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, 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, with 2,2,6,6-tetramethyl--3,5-heptadione is 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 reduce the direct effect between 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'] (2,2,6,6-tetramethyl--3,5-heptadione) 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, with 2,2,6,6-tetramethyl--3,5-heptadione is 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 obtains the phosphorescent emissions of different red emission wavelengths, obtains satisfied ruddiness.
And, acenaphthene-5-base benzodiazepine six-ring main body and 2,2,6,6-tetramethyl--3, the iridium metal complex that 5-heptadione part forms produces space steric effect to a certain extent, thereby reduces the direct effect between 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.
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.
Wherein, Ar is phthalazines, cinnolines, benzo pyrimidine or quinoxaline.
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 (PdCl
2(PPh
3)
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, 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, and after being dried, obtains 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 22～254 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 by chlorine bridge dipolymer and 2,2 in molar ratio, 6,6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, 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 2,2,6,6-tetramethyl--3, and 5-heptadione is fully dissolved as suitable.
Carbonate is sodium carbonate or salt of wormwood.
0.5:1.2～2 are by chlorine bridge dipolymer and 2,2,6 in molar ratio, 6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, adds carbonate, be heated to reflux state reaction 8～15 hours, chlorine bridge dipolymer and assistant ligand source 2,2,6,6-tetramethyl--3,5-heptadione generation ligand exchange, obtains red phosphorescent iridium metal complex after separation and purification, 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium.
Red phosphorescent two [1-(acenaphthene-5-yl) phthalazines-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) 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) 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 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 1-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-(acenaphthene-5-yl) phthalazines-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium
In argon atmosphere, by 0.79g (0.5mmol) 1-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer, 0.28g (1.5mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, is 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.45g, yield is 48.0%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 938.3 (M
+)
Ultimate analysis: C51H45IrN4O2
Theoretical value: C, 65.29; H, 4.83; Ir, 20.49; N, 5.97; O, 3.41;
Measured value: C, 65.24; H, 4.88; Ir, 20.55; N, 5.91; O, 3.42.
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'] (2,2,6,6-tetramethyl--3,5-heptadione) close 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, and end product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 628nm 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), record the Φ of end product
pL=0.26, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2
Red phosphorescent two [3-(acenaphthene-5-yl) cinnolines-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium.
Red phosphorescent two [3-(acenaphthene-5-yl) cinnolines-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(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, 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 and the mixed solution of sherwood oil are eluent, 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) 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 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 3-(acenaphthene-5-yl) cinnolines containing iridium dichloro dipolymer.
(3) two [3-(acenaphthene-5-yl) cinnolines-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium
In helium atmosphere, by 0.79g (0.5mmol) 3-(acenaphthene-5-yl) cinnolines containing iridium dichloro dipolymer, 0.37g (2mmol) 2, 2, 6, 6-tetramethyl--3, 5-heptadione and 0.69g (5mmol) salt of wormwood is dissolved in the 20mL dichloromethane solvent of degasification, be heated to reflux state reaction 15h, 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 1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final two [3-(acenaphthene-5-yl) cinnolines-N of pure red phosphorescence that obtain after dry, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.46g, yield is 49.0%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 938.3 (M
+)
Ultimate analysis: C51H45IrN4O2
Theoretical value: C, 65.29; H, 4.83; Ir, 20.49; N, 5.97; O, 3.41;
Measured value: C, 65.26; H, 4.89; Ir, 20.44; N, 6.04; O, 3.37.
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'] (2,2,6,6-tetramethyl--3,5-heptadione) 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 637nm 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium.
Red phosphorescent two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) 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, be naturally chilled to room temperature, 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 1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, and after being dried, obtains pure 2-(acenaphthene-5-yl) benzo pyrimidine 0.56g, and yield is 49.6%.Concrete reaction formula is as follows:
(2) 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 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 2-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer.
(3) two [2-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium
Under argon atmosphere, by 0.79g (0.5mmol) 2-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer, 0.28g (1.5mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 25mL2-ethoxy ethanol solvent of degasification, is 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.39g, yield is 41.6%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 938.3 (M
+)
Ultimate analysis: C51H45IrN4O2
Theoretical value: C, 65.29; H, 4.83; Ir, 20.49; N, 5.97; O, 3.41;
Measured value: C, 65.33; H, 4.85; Ir, 20.41; N, 5.96; O, 3.45.
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'] (2,2,6,6-tetramethyl--3,5-heptadione) 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 629nm 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=0.28.
Embodiment 4
Red phosphorescent two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium.
Red phosphorescent two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) 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, naturally be chilled to room temperature, 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 1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 4-(acenaphthene-5-yl) benzo pyrimidine 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, 85.15; 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) 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 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 4-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer.
(3) two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium
In argon atmosphere, by 0.79g (0.5mmol) 4-(acenaphthene-5-yl) benzo pyrimidine containing iridium dichloro dipolymer, 0.37g (2mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.69g (5mmol) salt of wormwood is dissolved in the 25mL2-methyl cellosolve solvent of degasification, is 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.42g, yield is 44.8%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 938.3 (M
+)
Ultimate analysis: C51H45IrN4O2
Theoretical value: C, 65.29; H, 4.83; Ir, 20.49; N, 5.97; O, 3.41;
Measured value: C, 65.22; H, 4.94; Ir, 20.45; N, 5.93; O, 3.46.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [4-(acenaphthene-5-yl) benzo pyrimidine-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) 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 627nm 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=0.32.
Embodiment 5
Red phosphorescent two [2-(acenaphthene-5-yl) quinoxaline-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium.
Red phosphorescent two [2-(acenaphthene-5-yl) quinoxaline-N, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) 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, be naturally chilled to room temperature, 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 1:4 and the mixed solution of sherwood oil are eluent, steaming desolventizes, and after being dried, obtains pure 2-(acenaphthene-5-yl) quinoxaline 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, 85.14; 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) 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 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 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 2-(acenaphthene-5-yl) quinoxaline containing iridium dichloro dipolymer.
(3) two [2-(acenaphthene-5-yl) quinoxaline-N, C of red phosphorescent
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of complex of iridium
In neon atmosphere, by 0.79g (0.5mmol) 2-(acenaphthene-5-yl) quinoxaline containing iridium dichloro dipolymer, 0.22g (1.2mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 25mL2-ethoxy ethanol solvent of degasification, is 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'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.34g, yield is 36.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 938.3 (M
+)
Ultimate analysis: C51H45IrN4O2
Theoretical value: C, 65.29; H, 4.83; Ir, 20.49; N, 5.97; O, 3.41;
Measured value: C, 65.26; H, 4.93; Ir, 20.40; N, 5.99; O, 3.42.
The material that the above-mentioned reaction of above data acknowledgement obtains is two [2-(acenaphthene-5-yl) quinoxaline-N, C of title complex
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 632nm 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=0.24.
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'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium, luminous material of main part is N, two carbazyl-4 of N'-, 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 7.1%, and maximum lumen efficiency is 6.2lm/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-Br 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, in embodiment, change, after separation and purification, obtain chlorine bridge dipolymer;
In the 3rd atmosphere of inert gases, 0.5:1.2～2 are by described chlorine bridge dipolymer and 2 in molar ratio, 2,6,6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, adds carbonate, be heated to obtain red phosphorescent iridium metal complex after reflux state reaction separation and purification in 8～15 hours, the structural formula of described red phosphorescent iridium metal complex is:
Wherein ,-Ar 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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