CN104178104A - Red organic electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device - Google Patents
Red organic electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device Download PDFInfo
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- CN104178104A CN104178104A CN201310192605.0A CN201310192605A CN104178104A CN 104178104 A CN104178104 A CN 104178104A CN 201310192605 A CN201310192605 A CN 201310192605A CN 104178104 A CN104178104 A CN 104178104A
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Abstract
The invention relates to a red organic electrophosphorescent material iridium metal complex, its preparation method and an organic electroluminescent device. The red organic electrophosphorescent material iridium metal complex has a structural formula as defined in the specification, wherein -Ar is as defined in the specification. By the use of the above red organic electrophosphorescent material iridium metal complex, electroluminescence performance of the organic electroluminescent device can be raised.
Description
Technical field
The present invention relates to a kind of electroluminescent organic material, particularly relate to a kind of ruddiness organic electromechanical phosphorescent material 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, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened 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, in building-up process, reaction conditions is gentle, 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 take 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.Yet 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 ruddiness organic electromechanical phosphorescent material iridium metal complex that can improve the luminescent properties of electroluminescent device.
A kind of preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex further, is provided.
A kind of organic electroluminescence device of ruddiness organic electromechanical phosphorescent material iridium metal complex is also provided.
A ruddiness organic electromechanical phosphorescent material iridium metal complex, its general structure is as follows:
Wherein ,-Ar is
or
A preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
In protective gas atmosphere; the Ar-Br that is 4:4.8～4:5 by mol ratio and acenaphthene-5-boric acid are dissolved in the first solvent, add the aqueous solution and the organic palladium of carbonate, carry out Suzuki linked reaction 8～12 hours; after separation and purification, obtain compd A, the structural formula of compd A is
wherein ,-Ar is
or
In protective gas atmosphere, the described compd A that is 2.2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent, are heated to reflux state reaction 22～25 hours, obtain compd B after separation and purification, and the structural formula of described compd B is:
In protective gas atmosphere; the described compd B of mol ratio 1:3～1:4 and described compd A are dissolved in the 3rd solvent; add carbonate; be heated to reflux state reaction 8～15 hours; after separation and purification, obtain ruddiness organic electromechanical phosphorescent material iridium metal complex, the general structure of described ruddiness organic electromechanical phosphorescent material iridium metal complex is:
Wherein ,-Ar is
or
In an embodiment, the mol ratio of described catalyzer and described Ar-Br is 4:100～6:100 therein, and the carbonate in the aqueous solution of described carbonate and the mol ratio of described Ar-Br are 2:1～3:1.
In an embodiment, described the first solvent is toluene or tetrahydrofuran (THF) therein, and described organic palladium is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium; Described the second solvent is 2-methyl cellosolve or cellosolvo; Described the 3rd solvent is 2-methyl cellosolve, cellosolvo or 1,2-ethylene dichloride.
Therein in an embodiment, after separation and purification, obtain in the step of compd A, the method of separation and purification is specially: after reacting completely, reaction solution naturally cools to room temperature, water and ethyl acetate extraction successively, by organic phase anhydrous magnesium sulfate drying, filter organic phase, then the solvent that rotation steaming removes in filtrate obtains oily crude product, the methylene dichloride that the volume ratio of take is 1:3～1:8 and sherwood oil mixed solution are eluent, by oily crude product silica gel column chromatography separating-purifying, steaming desolventizes, the compd A that must purify after being dried.
Therein in an embodiment, after separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, and reaction solution is cooled to room temperature, and reaction solution is successively with chloroform and distilled water extraction, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, and the acetone that the volume ratio of take is 1:5～1:10 and normal hexane mixed solution are eluent, crude product is carried out to silica gel column chromatography separating-purifying, obtain the compd B of purifying.
Therein in an embodiment, after separation and purification, obtain in the step of ruddiness organic electromechanical phosphorescent material iridium metal complex, the method of separation and purification is specially: after reacting completely, reaction solution naturally cools to room temperature, successively with chloroform and distilled water extraction, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, the methylene dichloride that the volume ratio of take is 1:8～1:12 and sherwood oil mixed solution are eluent, to crude product silica gel column chromatography separating-purifying, steaming desolventizes, the dry rear final pure ruddiness organic electromechanical phosphorescent material iridium metal complex that obtains.
In an embodiment, described carbonate is selected from least one in salt of wormwood and sodium carbonate therein.
A kind of organic electroluminescence device, comprise the transparent 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 N, two carbazyl-4 of N'-, 4'-dipyridyl and be entrained in described N, two carbazyl-4 of N'-, the ruddiness organic electromechanical phosphorescent material iridium metal complex in 4'-dipyridyl, described ruddiness organic electromechanical phosphorescent material iridium metal complex has following general structure:
Wherein ,-Ar is
or
It is cyclic metal complexes agent structure that above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex be take acenaphthene-5-base quinoline, atom centered by iridium, acenaphthene-5-base is incorporated in quinoline or isoquinoline 99.9 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 atoms metal, the self-quenching phenomenon that reduces triplet exciton, at room temperature just has very strong phosphorescent emissions; Simultaneously, the acenaphthenyl that has larger planar rigidity is 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 balance organic electroluminescence device, thereby improve the electroluminescent properties of organic electroluminescence device.
Accompanying drawing explanation
Preparation method's schema of the ruddiness organic electromechanical phosphorescent material iridium metal complex of Fig. 1 mono-embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is the utilizing emitted light spectrogram of the ruddiness organic electromechanical phosphorescent material iridium metal complex of embodiment 1 preparation.
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 have been 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, so the present invention is not subject to the restriction of following public concrete enforcement.
A ruddiness organic electromechanical phosphorescent material iridium metal complex, its structural formula is as follows:
Wherein ,-Ar is
or
It is cyclic metal complexes agent structure that above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex be take acenaphthene-5-base quinoline, atom centered by iridium, acenaphthene-5-base is incorporated in quinoline or isoquinoline 99.9 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 atoms metal, the self-quenching phenomenon that reduces triplet exciton, at room temperature just has very strong phosphorescent emissions; Simultaneously, the acenaphthenyl that has larger planar rigidity is 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, thereby improve the electroluminescent properties of device.
Refer to Fig. 1, the preparation method of the ruddiness organic electromechanical phosphorescent material iridium metal complex of an embodiment, comprises the steps:
Step S110: in protective gas atmosphere; the Ar-Br that is 4:4.8～4:5 by mol ratio and acenaphthene-5-boric acid are dissolved in the first solvent, add the aqueous solution and the organic palladium of carbonate, carry out Suzuki linked reaction 8～12 hours; after separation and purification, obtain compd A, the structural formula of compd A is
wherein ,-Ar is
or
Protective gas is argon gas, helium or neon.
The first solvent is toluene or tetrahydrofuran (THF) (THF).
Organic palladium is tetra-triphenylphosphine palladium (Pd (PPh
3)
4) or dichloro bi triphenyl phosphine palladium (Pd (PPh
3)
2cl
2).The consumption of the first solvent is so that Ar-Br and acenaphthene-5-boric acid are fully dissolved as suitable.Preferably, the solid-to-liquid ratio of acenaphthene-5-boric acid and the first solvent is 4.8mmol:25mL～5mmol:25mL.
Preferably, the mol ratio of catalyzer and Ar-Br is 4:100～6:100.
Carbonate in the aqueous solution of carbonate is sodium carbonate or salt of wormwood.In the aqueous solution of carbonate, the volumetric molar concentration of carbonate is 0.8mmol/mL～1mmol/mL.Carbonate in the aqueous solution of carbonate and the mol ratio of Ar-Br are 2:1～3:1.
The method that separation and purification obtains compd A is specially: after reacting completely, reaction solution naturally cools to room temperature, water and ethyl acetate extraction successively, by organic phase anhydrous magnesium sulfate drying, filter organic phase, the solvent that then rotation steaming removes in filtrate obtains oily crude product, the methylene dichloride that the volume ratio of take is 1:3～1:8 and sherwood oil mixed solution are eluent, by oily crude product silica gel column chromatography separating-purifying, except desolventizing, the compd A after must purifying after being dried.
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.
The reaction formula of above-mentioned Suzuki linked reaction is:
Step S120: in protective gas atmosphere; the described compd A that is 2.2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent; be heated to reflux state reaction 22～25 hours, obtain compd B after separation and purification, the structural formula of described compd B is:
Protective gas is argon gas, helium or neon.
The second solvent is 2-methyl cellosolve or cellosolvo.The consumption of the second solvent is so that compd A and three hydration iridous chlorides are fully dissolved as suitable.Preferably, the solid-to-liquid ratio of three hydration iridous chlorides and the second solvent is 1mmol:25mL～1mmol:15mL.
After separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, reaction solution is cooled to room temperature, reaction solution is successively with chloroform and distilled water extraction, and organic phase anhydrous magnesium sulfate drying, filters, steaming desolventizes and obtains crude product, the acetone that the volume ratio of take is 1:5～1:10 and normal hexane mixed solution are eluent, and crude product is carried out to silica gel column chromatography separating-purifying, obtain the compd B of purifying.
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.
The reaction formula of this step is as follows:
Step S130: in protective gas atmosphere; the compd B of mol ratio 1:3～1:4 and compd A are dissolved in the 3rd solvent; add carbonate; be heated to reflux state reaction 8～15 hours; after separation and purification, obtain ruddiness organic electromechanical phosphorescent material iridium metal complex, the structural formula of ruddiness organic electromechanical phosphorescent material iridium metal complex is:
Wherein ,-Ar is
or
Protective gas is argon gas, helium or neon.
The 3rd solvent is 2-methyl cellosolve, cellosolvo or 1,2-ethylene dichloride.The consumption of the 3rd solvent is so that compd B and methyl ethyl diketone are fully dissolved as suitable.Preferably, the ratio of compd A and the second solvent is 0.5mmol:25mL～0.5mmol:20mL.
Carbonate is sodium carbonate or salt of wormwood.The mol ratio of carbonate and compd A is 5:0.5.
The method of separation and purification is specially: 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, reaction solution naturally cools to room temperature, with chloroform and distilled water extraction, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, the methylene dichloride that the volume ratio of take is 1:8～1:12 and sherwood oil mixed solution are eluent, to crude product silica gel column chromatography separating-purifying, steaming desolventizes, the dry rear final pure ruddiness organic electromechanical phosphorescent material 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.
The reaction formula of this step is as follows:
Preparation method's reaction conditions of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex is gentle, and 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 transparent anode 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electronic injection buffer layer 307 and the negative electrode 308 that stack gradually.
The material of transparent anode 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electronic injection buffer layer 307 and negative electrode 308 is respectively the common used material of this area.For example, the material of anode 301 is that the material of tin indium oxide (ITO), hole injection layer 302 is 4,4', the material of 4''-tri-(N-(naphthalene-2-yl)-N-phenyl amino) triphenylamine (2-TNATA), hole transmission layer 303 is N, two (1-the naphthyl)-N of N'-, the material of N '-phenylbenzene benzidine (NPB), hole blocking layer 305 is 2,9-dimethyl-4, the material of 7-phenylbenzene-phenanthrolene (BCP), electron transfer layer 306 is three (oxine) aluminium (Alq
3), the material of electronic injection buffer layer 307 is that the material of oxine lithium (Liq), negative electrode 308 is metallic aluminium (Al).
The material of luminescent layer 304 comprises takes N, two carbazyl-4 of N'-, 4'-dipyridyl and be entrained in described N, two carbazyl-4 of N'-, the ruddiness organic electromechanical phosphorescent material iridium metal complex in 4'-dipyridyl.
Above-mentioned ruddiness organic electromechanical phosphorescent material 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 ruddiness organic electromechanical phosphorescent material iridium metal complex that contains high color purity in luminescent layer 304, 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 should be noted that, the material of above-mentioned organic electroluminescence device Anodic 301, hole injection layer 302, hole transmission layer 303, hole blocking layer 305, electron transfer layer 306, electronic injection buffer layer 307 and negative electrode 308 also can be other common used materials in the industry.
It is below specific embodiment.
Embodiment 1
Title complex three [2-(acenaphthene-5-yl) quinoline-N, C
2'] close synthesizing of iridium
Three [2-(acenaphthene-5-yl) quinoline-N, C
2'] structural formula that closes iridium is as follows:
(1) 2-(acenaphthene-5-yl) quinoline is synthetic
Under argon shield; 0.83g (4mmol) 2-bromoquinoline, 0.95g (4.8mmol) acenaphthene-5-boric acid and 0.28g (0.24mmol) tetra-triphenylphosphine palladium are dissolved in 25mL tetrahydrofuran (THF), drip 10mL containing the aqueous solution of 1.10g (8mmol) salt of wormwood subsequently in reaction system.Heating, stirs under reflux state and carries out Suzuki reaction 10h.After reacting completely, reaction solution is chilled to room temperature naturally, by 15mL water and 15mL ethyl acetate, extract 3 times successively, by organic phase anhydrous magnesium sulfate drying, filter organic phase, rotation is steamed the solvent removing in filtrate and is obtained oily crude product, the methylene dichloride that the volume ratio of take is 1:3 and sherwood oil mixed solution are eluent, and by oily crude product silica gel column chromatography separating-purifying, steaming desolventizes, after dry, obtain pure solid matter 0.67g, yield is 59.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 281.1 (M
+)
Ultimate analysis: C21H15N
Theoretical value: C, 89.65; H, 5.37; N, 4.98;
Measured value: C, 89.58; H, 5.49; N, 4.93.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(acenaphthene-5-yl) quinoline.
(2) the synthesizing containing iridium dichloro dipolymer of 2-(acenaphthene-5-yl) quinoline
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 0.70g (2.5mmol) 2-(acenaphthene-5-yl) quinoline is dissolved in 15mL2-ethoxy ethanol, is heated to reflux state reaction 24h.Be chilled to after room temperature, reaction mixture extracts 3 times with 10mL chloroform and 10mL distilled water successively, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, and the acetone that the volume ratio of take is 1:5 and normal hexane mixed solution are eluent, and crude product is carried out to silica gel column chromatography separating-purifying, obtain pure solid 0.30g, yield is 38.0%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1576.3 (M
+)
Ultimate analysis: C84H56Cl2Ir2N4
Theoretical value: C, 63.99; H, 3.58; Cl, 4.50; Ir, 24.38; N, 3.55;
Measured value: C, 63.93; H, 3.65; Cl, 4.54; Ir, 24.35; N, 3.53.
The resulting material of the above-mentioned reaction of above data acknowledgement be 2-(acenaphthene-5-yl) quinoline containing iridium dichloro dipolymer.
(3) ruddiness organic electromechanical phosphorescent material iridium metal complex three [2-(acenaphthene-5-yl) quinoline-N, C
2'] close synthesizing of iridium
Under argon shield; the main part of 0.79g (0.5mmol) be 2-(acenaphthene-5-yl) quinoline containing iridium dichloro dipolymer; 0.42g (1.5mmol) 2-(acenaphthene-5-yl) quinoline and 0.53g (5mmol) sodium carbonate are dissolved in the 20mL2-ethoxy ethanol solvent of degasification, are heated to reflux state reaction 15h.After reacting completely, be naturally chilled to room temperature, with 10mL chloroform and 10mL distilled water, extract 3 times successively.Organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed to desolventize and obtained crude product.The methylene dichloride that the volume ratio of take is 1:8 and sherwood oil mixed solution are eluent, crude product silica gel column chromatography separating-purifying, and steaming desolventizes, the dry rear final pure substance 0.41g that obtains, yield is 39.7%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1033.3 (M
+)
Ultimate analysis: C63H42IrN3
Theoretical value: C, 73.23; H, 4.10; Ir, 18.60; N, 4.07;
Measured value: C, 73.18; H, 4.19; Ir, 18.62; N, 4.01.
The resulting material of the above-mentioned reaction of above data acknowledgement is ruddiness organic electromechanical phosphorescent material iridium metal complex three [2-(acenaphthene-5-yl) quinoline-N, C
2'] close iridium.
Fig. 3 is above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex three [2-(acenaphthene-5-yl) quinoline-N, C
2'] close the utilizing emitted light spectrogram 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, ruddiness organic electromechanical phosphorescent material iridium metal complex three [2-(acenaphthene-5-yl) quinoline-N, C
2'] close iridium CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M), at 625nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in 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=0.20, ruddiness organic electromechanical phosphorescent material iridium metal complex three [2-(acenaphthene-5-yl) quinoline-N, the C of visible the present embodiment
2'] close iridium and there is higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2
Title complex three [1-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close synthesizing of iridium
Three [1-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] structural formula that closes iridium is as follows:
(1) 1-(acenaphthene-5-yl) isoquinoline 99.9 is synthetic
Under argon shield; 0.83g (4mmol) 1-bromo-isoquinoline, 0.99g (5mmol) acenaphthene-5-boric acid and 0.23g (0.20mmol) tetra-triphenylphosphine palladium are dissolved in 25mL THF, drip 10mL containing the aqueous solution of 1.38g (10mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 12h under reflux state.After reacting completely, be naturally chilled to room temperature, by 15mL water and 15mL ethyl acetate, extract 3 times successively.Organic phase anhydrous magnesium sulfate drying, filters.Rotation is steamed the solvent removing in filtrate and is obtained oily crude product.The methylene dichloride that the volume ratio of take is 1:5 and sherwood oil mixed solution are eluent, oily crude product silica gel column chromatography separating-purifying,, steaming desolventizes, and after being dried, obtains pure solid matter 0.62g, and yield is 55.1%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 281.1 (M
+)
Ultimate analysis: C21H15N
Theoretical value: C, 89.65; H, 5.37; N, 4.98;
Measured value: C, 89.61; H, 5.44; N, 4.95.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-(acenaphthene-5-yl) isoquinoline 99.9.
(2) the synthesizing containing iridium dichloro dipolymer of 1-(acenaphthene-5-yl) isoquinoline 99.9
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 0.62g (2.2mmol) 1-(acenaphthene-5-yl) isoquinoline 99.9 is dissolved in 20mL2-ethoxy ethanol, is heated to reflux state reaction 22h.Be chilled to after room temperature, reaction mixture extracts 3 times with 10mL chloroform and 10mL distilled water successively, and organic phase anhydrous magnesium sulfate drying filters, and steams to desolventize to obtain crude product.The acetone that the volume ratio of take is 1:6 and normal hexane mixed solution are eluent, and crude product is carried out to silica gel column chromatography separating-purifying, obtain pure solid 0.28g, and yield is 35.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1576.3 (M
+)
Ultimate analysis: C84H56Cl2Ir2N4
Theoretical value: C, 63.99; H, 3.58; Cl, 4.50; Ir, 24.38; N, 3.55;
Measured value: C, 63.93; H, 3.65; Cl, 4.54; Ir, 24.35; N, 3.53.
The resulting material of the above-mentioned reaction of above data acknowledgement be 1-(acenaphthene-5-yl) isoquinoline 99.9 containing iridium dichloro dipolymer.
(3) ruddiness organic electromechanical phosphorescent material iridium metal complex three [1-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close synthesizing of iridium
Under argon shield; the main part of 0.79g (0.5mmol) be 1-(acenaphthene-5-yl) isoquinoline 99.9 containing iridium dichloro dipolymer; 0.56g (2mmol) 1-(acenaphthene-5-yl) isoquinoline 99.9 and 0.42g (4mmol) salt of wormwood are dissolved in the 20mL2-methyl cellosolve solvent of degasification, are heated to reflux state reaction 8h.After reacting completely, be naturally chilled to room temperature, with 10mL chloroform and 10mL distilled water, extract 3 times successively.Organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized to obtain crude product.The methylene dichloride that the volume ratio of take is 1:10 and sherwood oil mixed solution are eluent, crude product silica gel column chromatography separating-purifying, and steaming desolventizes, the dry rear final pure substance 0.46g that obtains, yield is 44.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1033.3 (M
+)
Ultimate analysis: C63H42IrN3
Theoretical value: C, 73.23; H, 4.10; Ir, 18.60; N, 4.07;
Measured value: C, 73.27; H, 4.05; Ir, 18.66; N, 4.02.
The resulting material of the above-mentioned reaction of above data acknowledgement is ruddiness organic electromechanical phosphorescent material iridium metal complex three [1-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 635nm 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=0.25.
Embodiment 3
Title complex three [3-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close synthesizing of iridium
Three [3-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] structural formula that closes iridium is as follows:
(1) 3-(acenaphthene-5-yl) isoquinoline 99.9 is synthetic
Under argon shield; 0.83g (4mmol) 3-bromo-isoquinoline, 0.97g (4.9mmol) acenaphthene-5-boric acid and 0.12g (0.16mmol) dichloro bi triphenyl phosphine palladium are dissolved in 20mL toluene, drip 10mL containing the aqueous solution of 1.27g (12mmol) sodium carbonate subsequently in reaction system.Heating, stirring reaction 8h under reflux state.After reacting completely, be naturally chilled to room temperature, by 15mL water and 15mL ethyl acetate, extract 3 times successively.Organic phase anhydrous magnesium sulfate drying, filters.Rotation is steamed the solvent removing in filtrate and is obtained oily crude product.The methylene dichloride that the volume ratio of take is 1:8 and sherwood oil mixed solution are eluent, oily crude product silica gel column chromatography separating-purifying, and steaming desolventizes, and after being dried, obtains pure solid matter 0.65g, and yield is 57.8%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 281.1 (M
+)
Ultimate analysis: C21H15N
Theoretical value: C, 89.65; H, 5.37; N, 4.98;
Measured value: C, 89.57; H, 5.42; N, 5.01.
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(acenaphthene-5-yl) isoquinoline 99.9.
(2) the synthesizing containing iridium dichloro dipolymer of 3-(acenaphthene-5-yl) isoquinoline 99.9
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 0.84g (3mmol) 3-(acenaphthene-5-yl) isoquinoline 99.9 is dissolved in 25mL2-ethoxy ethanol, is heated to reflux state reaction 25h.Be chilled to after room temperature, reaction mixture extracts 3 times with 10mL chloroform and 10mL distilled water successively, and organic phase anhydrous magnesium sulfate drying filters, and steams and desolventizes to obtain crude product.The acetone that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, and crude product is carried out to silica gel column chromatography separating-purifying, obtain pure solid 0.32g, and yield is 40.6%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1576.3 (M
+)
Ultimate analysis: C84H56Cl2Ir2N4
Theoretical value: C, 63.99; H, 3.58; Cl, 4.50; Ir, 24.38; N, 3.55;
Measured value: C, 63.95; H, 3.63; Cl, 4.54; Ir, 24.31; N, 3.57.
The resulting material of the above-mentioned reaction of above data acknowledgement be 3-(acenaphthene-5-yl) isoquinoline 99.9 containing iridium dichloro dipolymer.
(3) ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close synthesizing of iridium
Under argon shield; the main part of 0.79g (0.5mmol) be 3-(acenaphthene-5-yl) isoquinoline 99.9 containing iridium dichloro dipolymer; 0.49g (1.75mmol) 3-(acenaphthene-5-yl) isoquinoline 99.9 and 0.83g (6mmol) sodium carbonate are dissolved in the 25mL1 of degasification; in 2-ethylene dichloride solvent, be heated to reflux state reaction 15h.After reacting completely, be naturally chilled to room temperature, with 10mL chloroform and 10mL distilled water, extract 3 times successively.Organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized to obtain crude product.The methylene dichloride that the volume ratio of take is 1:12 and sherwood oil mixed solution are eluent, crude product silica gel column chromatography separating-purifying, and steaming desolventizes, the dry rear final pure substance 0.47g that obtains, yield is 45.5%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1033.3 (M
+)
Ultimate analysis: C63H42IrN3
Theoretical value: C, 73.23; H, 4.10; Ir, 18.60; N, 4.07;
Measured value: C, 73.20; H, 4.15; Ir, 18.63; N, 4.02.
The resulting material of the above-mentioned reaction of above data acknowledgement is ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-(acenaphthene-5-yl) isoquinoline 99.9-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M) is at 620nm 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=0.15.
Embodiment 4
An organic electroluminescence device, comprises the 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.
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 transparent anode, by vacuum evaporation, preparing successively thickness on anode 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 three [2-(acenaphthene-5-yl) quinoline-N of embodiment 1 preparation, C
2'] closing 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 ratio of luminous guest materials and luminous material of main part is 8:100.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, negative electrode as 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).
By Keithley source measuring system (Keithley2400Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, 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 10.1%, and maximum lumen efficiency is 7.1lm/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 ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, its general structure is as follows:
Wherein ,-Ar is
or
2. a preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, comprises the steps:
In protective gas atmosphere; the Ar-Br that is 4:4.8～4:5 by mol ratio and acenaphthene-5-boric acid are dissolved in the first solvent, add the aqueous solution and the organic palladium of carbonate, carry out Suzuki linked reaction 8～12 hours; after separation and purification, obtain compd A, the structural formula of compd A is
wherein ,-Ar is
In protective gas atmosphere, the described compd A that is 2.2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent, are heated to reflux state reaction 22～25 hours, obtain compd B after separation and purification, and the structural formula of described compd B is:
In protective gas atmosphere; the described compd B of mol ratio 1:3～1:4 and described compd A are dissolved in the 3rd solvent; add carbonate; be heated to reflux state reaction 8～15 hours; after separation and purification, obtain ruddiness organic electromechanical phosphorescent material iridium metal complex, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex is:
Wherein ,-Ar is
or
3. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, it is characterized in that, the mol ratio of described catalyzer and described Ar-Br is 4:100～6:100, and the carbonate in the aqueous solution of described carbonate and the mol ratio of described Ar-Br are 2:1～3:1.
4. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, is characterized in that, described the first solvent is toluene or tetrahydrofuran (THF), and described organic palladium is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium; Described the second solvent is 2-methyl cellosolve or cellosolvo; Described the 3rd solvent is 2-methyl cellosolve, cellosolvo or 1,2-ethylene dichloride.
5. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain in the step of compd A, the method of separation and purification is specially: after reacting completely, reaction solution naturally cools to room temperature, water and ethyl acetate extraction successively, by organic phase anhydrous magnesium sulfate drying, filter organic phase, then the solvent that rotation steaming removes in filtrate obtains oily crude product, the methylene dichloride that the volume ratio of take is 1:3～1:8 and sherwood oil mixed solution are eluent, to oily crude product silica gel column chromatography separating-purifying, steaming desolventizes, the compd A that must purify after dry.
6. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, reaction solution is cooled to room temperature, reaction solution is successively with chloroform and distilled water extraction, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, the acetone that the volume ratio of take is 1:5～1:10 and normal hexane mixed solution are eluent, and crude product is carried out to silica gel column chromatography separating-purifying, obtain the compd B of purifying.
7. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, it is characterized in that, after separation and purification, obtain in the step of ruddiness organic electromechanical phosphorescent material iridium metal complex, the method of separation and purification is specially: after reacting completely, reaction solution naturally cools to room temperature, successively with chloroform and distilled water extraction, organic phase anhydrous magnesium sulfate drying, filter, steaming desolventizes and obtains crude product, the methylene dichloride that the volume ratio of take is 1:8～1:12 and sherwood oil mixed solution are eluent, to crude product silica gel column chromatography separating-purifying, steaming desolventizes, the dry rear final pure ruddiness organic electromechanical phosphorescent material iridium metal complex that obtains.
8. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 2, is characterized in that, described carbonate is selected from least one in salt of wormwood and sodium carbonate.
9. an organic electroluminescence device, comprise the transparent anode, the hole injection layer that stack gradually, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electronic injection buffer layer and negative electrode, it is characterized in that, the material of described luminescent layer comprises takes N, two carbazyl-4 of N'-, 4'-dipyridyl and be entrained in described N, two carbazyl-4 of N'-, ruddiness organic electromechanical phosphorescent material iridium metal complex in 4'-dipyridyl, described ruddiness organic electromechanical phosphorescent material iridium metal complex has following general structure:
Wherein ,-Ar is
or
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| KR20120031771A (en) * | 2010-09-27 | 2012-04-04 | 삼성모바일디스플레이주식회사 | Metal complex compound and organic light emitting diode device including the same |
| CN102649904A (en) * | 2011-02-28 | 2012-08-29 | 海洋王照明科技股份有限公司 | Iridium-containing organic electroluminescent material, preparation method thereof and organic electroluminescent device |
| CN102649903A (en) * | 2011-02-28 | 2012-08-29 | 海洋王照明科技股份有限公司 | Iridium-containing organic electroluminescent material, preparation method thereof and organic electroluminescent device |
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| KR20120031771A (en) * | 2010-09-27 | 2012-04-04 | 삼성모바일디스플레이주식회사 | Metal complex compound and organic light emitting diode device including the same |
| CN102649904A (en) * | 2011-02-28 | 2012-08-29 | 海洋王照明科技股份有限公司 | Iridium-containing organic electroluminescent material, preparation method thereof and organic electroluminescent device |
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