CN104178114A - 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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- CN104178114A CN104178114A CN201310194951.2A CN201310194951A CN104178114A CN 104178114 A CN104178114 A CN 104178114A CN 201310194951 A CN201310194951 A CN 201310194951A CN 104178114 A CN104178114 A CN 104178114A
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- 0 *c1ccc2c3c1cccc3CC2 Chemical compound *c1ccc2c3c1cccc3CC2 0.000 description 1
- QOAMJAPIXSKLCA-UHFFFAOYSA-N C(Cc1ccc2-c(nn3)c(cccc4)c4c3Oc3ccccc3)c3c1c2ccc3 Chemical compound C(Cc1ccc2-c(nn3)c(cccc4)c4c3Oc3ccccc3)c3c1c2ccc3 QOAMJAPIXSKLCA-UHFFFAOYSA-N 0.000 description 1
- NAUJHAZPVFXXKR-UHFFFAOYSA-N C=[Br]c(nn1)c(cccc2)c2c1OC1=CC=CCC1 Chemical compound C=[Br]c(nn1)c(cccc2)c2c1OC1=CC=CCC1 NAUJHAZPVFXXKR-UHFFFAOYSA-N 0.000 description 1
- ZMSMPLUOKYMKGZ-UHFFFAOYSA-N CC[O](C)c1c(cccc2)c2c(-c2ccc3c4c2cccc4CC3)nn1 Chemical compound CC[O](C)c1c(cccc2)c2c(-c2ccc3c4c2cccc4CC3)nn1 ZMSMPLUOKYMKGZ-UHFFFAOYSA-N 0.000 description 1
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 -R is alkyl having a general formula of -CnH<2n+1>, alkoxy having a general formula of -OCnH<2n+1>, benzyl or phenoxyl, and the n is an integer ranging from 1 to 20. The red phosphorescence iridium complexes have strong phosphorescence emission at room temperature. Introduction of the alkyl of different chain lengths and the alkoxy of different chain lengths can increase solubility of the materials in organic solvents and control light-emitting wavelengths of the materials. The red phosphorescence iridium complexes are respectively provided with acenaphthenyl and a phthalazine ring structure that are high in planar rigidity, and the benzyl and the phenoxyl which are large groups are also introduced, thus facilitating phosphorescence luminescence, controlling the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels of the materials, facilitating charge transfer in balancing devices, and improving electroluminescence properties of the 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, 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 red phosphorescent iridium metal complex that can improve the luminescent properties of 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 red phosphorescent iridium metal complex, structural formula is as follows:
Wherein ,-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20.
A preparation method for red phosphorescent iridium metal complex, comprises the steps:
In the first atmosphere of inert gases, for 4:4.8～5,1-R-4-bromine phthalazines 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 ligand 1-R-4-(acenaphthene-5-yl) phthalazines, wherein, described-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20;
In the second atmosphere of inert gases, be that 2.5～3:1 is dissolved in described ring master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines 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 main part and be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer;
In the 3rd atmosphere of inert gases, in molar ratio 0.5:1.5～2 by described main part be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer and 2,2,6,6-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:
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 0.2～0.24:4.8～5 therein.
Therein in an embodiment, after separation and purification, obtain encircling in the step of master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines, 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, the methylene dichloride that the volume ratio of take is 1:3～1:10 and the mixed solution of sherwood oil are eluent, and steaming desolventizes, and after being dried, obtain pure ring master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines.
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, the acetone that the volume ratio of take is 1:5～1:15 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, the methylene dichloride that the volume ratio of take is 1:10～1:22 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.
It is cyclic metal complexes agent structure that above-mentioned red phosphorescent iridium metal complex be take 4-(acenaphthene-5-yl) phthalazines, with 2,2,6,6-tetramethyl--3,5-heptadione is assistant ligand, acenaphthene-5-base is incorporated in phthalazines 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 atoms metal, the self-quenching phenomenon that reduces triplet exciton, at room temperature just has very strong phosphorescent emissions; And the alkyl of different chain length, the introducing of alkoxyl group, can not only increase the solvability of this material in organic solvent, can also effectively control the emission wavelength of material; Simultaneously, the acenaphthenyl and the phthalazines ring structure that have respectively larger planar rigidity, add the introducing of phenyl, phenoxy group macoradical, be conducive on the one hand the luminous of phosphorescence, 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.
Accompanying drawing explanation
Fig. 1 is preparation method's the schema of the red phosphorescent iridium metal complex of an embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is two [1-methyl-4-(acenaphthene-5-yl) phthalazines-N, C of the red phosphorescent of embodiment 1 preparation
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 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 red phosphorescent iridium metal complex, its structural formula is as follows:
Wherein ,-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20.
General formula is-C
nh
2n+1alkyl be straight chained alkyl or branched-chain alkyl.General formula is-OC
nh
2n+1alkoxyl group be straight chain alkoxyl group or branched alkoxy.
It is cyclic metal complexes agent structure that above-mentioned red phosphorescent iridium metal complex be take 4-(acenaphthene-5-yl) phthalazines, with 2,2,6,6-tetramethyl--3,5-heptadione is assistant ligand, acenaphthene-5-base is incorporated in phthalazines 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 atoms metal, the self-quenching phenomenon that reduces triplet exciton, at room temperature just has very strong phosphorescent emissions.
And the alkyl of different chain length, the introducing of alkoxyl group, can not only increase the solvability of material in organic solvent, can also effectively control the emission wavelength of material.
Simultaneously, the acenaphthenyl and the phthalazines ring structure that have respectively larger planar rigidity, add the introducing of phenyl, phenoxy group macoradical, be conducive on the one hand the luminous of phosphorescence, 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 4:4.8～5,1-R-4-bromine phthalazines 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 ligand 1-R-4-(acenaphthene-5-yl) phthalazines.
Wherein ,-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20.
General formula is-C
nh
2n+1alkyl be straight chained alkyl or branched-chain alkyl.General formula is-OC
nh
2n+1alkoxyl group be straight chain alkoxyl group or branched alkoxy.
The first rare gas element is argon gas, helium or neon.
The first solvent is toluene or tetrahydrofuran (THF) (THF).The consumption of the first solvent is so that 1-R-4-bromine phthalazines 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 0.2～0.24:4.8～5.
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 4:4.8～5,1-R-4-bromine phthalazines and acenaphthene-5-boric acid are dissolved in the first solvent in molar ratio, add catalyzer and carbonate solution, heating, under reflux state, stir 8～12 hours, carry out Suzuki linked reaction, after separation and purification, obtain encircling master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines.
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, with suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed except the solvent in filtrate.Oily crude product silica gel column chromatography separating-purifying, the methylene dichloride that the volume ratio of take is 1:3～1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, and after being dried, obtains pure ring master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines.
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 2.5～3:1 will encircle master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines and three hydration iridous chlorides are dissolved in the second solvent in molar ratio, be heated to reflux state reaction 22～25 hours, after separation and purification, obtain main part and be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium 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 ligand 1-R-4-(acenaphthene-5-yl) phthalazines and three hydration iridous chlorides are fully dissolved as suitable.
Be that 2.5～3:1 will encircle master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines and three hydration iridous chloride (IrCl in molar ratio
33H
2o) be dissolved in the second solvent, be heated to reflux state reaction 22～25 hours, after separation and purification, obtain main part and be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer, 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, the acetone that the volume ratio of take is 1:5～1:15 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium 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, in molar ratio 0.5:1.2～2 by main part be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer and 2,2,6,6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, adds 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, main part be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer and 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:
In the red phosphorescent iridium metal complex obtaining after separation and purification ,-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20.
General formula is-C
nh
2n+1alkyl be straight chained alkyl or branched-chain alkyl.General formula is-OC
nh
2n+1alkoxyl group be straight chain alkoxyl group or branched alkoxy.
The method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized.Crude product silica gel column chromatography separating-purifying, the methylene dichloride that the volume ratio of take is 1:10～1:22 and the mixed solution of sherwood oil are eluent, 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 of above-mentioned red phosphorescent 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 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-methyl-4-(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-methyl-4-(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-methyl-4-(acenaphthene-5-yl) phthalazines is synthetic
In argon atmosphere, 0.89g (4mmol) 1-methyl-4-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 10mL containing the aqueous solution of 0.85g (8mmol) sodium carbonate subsequently, heating, stirring 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 that the volume ratio of take is 1:3 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 1-methyl-4-(acenaphthene-5-yl) phthalazines 0.71g, yield is 59.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 296.1 (M
+)
Ultimate analysis: C21H16N2
Theoretical value: C, 85.11; H, 5.44; N, 9.45;
Measured value: C, 85.17; H, 5.41; N, 9.42.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-methyl-4-(acenaphthene-5-yl) phthalazines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 1-methyl-4-(acenaphthene-5-yl) phthalazines
In argon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.74g (2.5mmol) 1-methyl-4-(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, the acetone that the volume ratio of take is 1:5 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-methyl-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer 0.27g, yield is 33.02%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1637.4 (M
+)
Ultimate analysis: C84H60Cl2Ir2N8
Theoretical value: C, 61.64; H, 3.69; Cl, 4.33; Ir, 23.49; N, 6.85;
Measured value: C, 61.67; H, 3.62; Cl, 4.38; Ir, 23.45; N, 6.88.
The resulting material of the above-mentioned reaction of above data acknowledgement be main part be 1-methyl-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-methyl-4-(acenaphthene-5-yl) phthalazines-N, C of red phosphorescent
2'] (methyl ethyl diketone) close the synthetic of iridium
In argon atmosphere, by the main part of 0.82g (0.5mmol) be 1-methyl-4-(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, be heated to reflux state reaction 10h, 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/sherwood oil mixed solution that the volume ratio of take is 1:10 is eluent, steaming desolventizes, final two [1-methyl-4-(acenaphthene-5-yl) phthalazines-N of pure red phosphorescence that obtain after dry, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.44g, yield is 45.4%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 968.4 (M
+)
Ultimate analysis: C53H51IrN4O2
Theoretical value: C, 65.75; H, 5.31; Ir, 19.85; N, 5.79; O, 3.30;
Measured value: C, 65.72; H, 5.36; Ir, 19.81; N, 5.84; O, 3.27.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [1-methyl-4-(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 2, 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), at 628nm 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=0.30, 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 [1-methoxyl group-4-(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-methoxyl group-4-(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-methoxyl group-4-(acenaphthene-5-yl) phthalazines is synthetic
In neon atmosphere, 0.96g (4mmol) 1-methoxyl group-4-bromine phthalazines, 0.99g (5mmol) acenaphthene-5-boric acid and 0.28g (0.24mmol) tetra-triphenylphosphine palladium are dissolved in 25mL THF, in reaction system, drip 10mL containing the aqueous solution of 1.38g (10mmol) salt of wormwood subsequently, heating, stirring reaction 12h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, with suitable quantity of water and ethyl acetate extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed except the solvent in filtrate, oily crude product silica gel column chromatography separating-purifying, the methylene dichloride that the volume ratio of take is 1:5 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines 0.71g, yield is 56.8%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C21H16N2O
Theoretical value: C, 80.75; H, 5.16; N, 8.97; O, 5.12;
Measured value: C, 80.72; H, 5.19; N, 8.93; O, 5.16.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines
In neon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.94g (3mmol) 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines are dissolved in 20mL2-methyl cellosolve, be heated to reflux state reaction 22h.Reaction finishes, and reaction solution is chilled to after room temperature, chloroform and distilled water extracted several times for reaction solution, and organic phase anhydrous magnesium sulfate drying, filters, and steaming desolventizes.Crude product is carried out to silica gel column chromatography separating-purifying, and the acetone that the volume ratio of take is 1:8 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer 0.26g, yield is 30.6%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1701.3 (M
+)
Ultimate analysis: C84H60Cl2Ir2N8O4
Theoretical value: C, 59.32; H, 3.56; Cl, 4.17; Ir, 22.60; N, 6.59; O, 3.76;
Measured value: C, 59.35; H, 3.51; Cl, 4.15; Ir, 22.66; N, 6.53; O, 3.80.
The resulting material of the above-mentioned reaction of above data acknowledgement be main part be 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-methoxyl group-4-(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 neon atmosphere, by the main part of 0.85g (0.5mmol) be 1-methoxyl group-4-(acenaphthene-5-yl) phthalazines 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, 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 that the volume ratio of take is 1:15 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [1-methoxyl group-4-(acenaphthene-5-yl) phthalazines-N, the C of obtaining after dry
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.40g, yield is 40.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1000.3 (M
+)
Ultimate analysis: C53H51IrN4O4
Theoretical value: C, 63.64; H, 5.14; Ir, 19.22; N, 5.60; O, 6.40;
Measured value: C, 63.68; H, 5.08; Ir, 19.25; N, 5.63; O, 6.36.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [1-methoxyl group-4-(acenaphthene-5-yl) phthalazines-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 625nm 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
Red phosphorescent two [1-phenyl-4-(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-phenyl-4-(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-phenyl-4-(acenaphthene-5-yl) phthalazines is synthetic
In helium atmosphere, 1.14g (4mmol) 1-phenyl-4-bromine phthalazines, 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 10mL containing the aqueous solution of 1.06g (10mmol) sodium carbonate subsequently.Heating, stirring reaction 8h 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 that the volume ratio of take is 1:8 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 1-phenyl-4-(acenaphthene-5-yl) phthalazines 0.71g, yield is 49.5%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 358.1 (M
+)
Ultimate analysis: C26H18N2
Theoretical value: C, 87.12; H, 5.06; N, 7.82;
Measured value: C, 87.16; H, 5.01; N, 7.83.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-phenyl-4-(acenaphthene-5-yl) phthalazines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 1-phenyl-4-(acenaphthene-5-yl) phthalazines
In helium atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 1.08g (3mmol) 1-phenyl-4-(acenaphthene-5-yl) phthalazines 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, the acetone that the volume ratio of take is 1:12 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-phenyl-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer 0.27g, yield is 28.6%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1885.4 (M
+)
Ultimate analysis: C104H68Cl2Ir2N8
Theoretical value: C, 66.26; H, 3.64; Cl, 3.76; Ir, 20.39; N, 5.94;
Measured value: C, 66.23; H, 3.69; Cl, 3.73; Ir, 20.44; N, 5.91.
The resulting material of the above-mentioned reaction of above data acknowledgement be main part be 1-phenyl-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-phenyl-4-(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 helium atmosphere, by the main part of 0.94g (0.5mmol) be 1-phenyl-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer, 0.37g (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 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 that the volume ratio of take is 1:20 and the mixed solution of sherwood oil are eluent, steaming desolventizes, final pure red phosphorescence two [1-phenyl-4-(acenaphthene-5-yl) phthalazines-N, the C of obtaining after dry
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.33g, yield is 30.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1092.4 (M
+)
Ultimate analysis: C63H55IrN4O2
Theoretical value: C, 69.27; H, 5.07; Ir, 17.60; N, 5.13; O, 2.93;
Measured value: C, 69.23; H, 5.13; Ir, 17.55; N, 5.18; O, 2.91.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [1-phenyl-4-(acenaphthene-5-yl) phthalazines-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=0.32.
Embodiment 4
Red phosphorescent two [1-phenoxy group-4-(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-phenoxy group-4-(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-phenoxy group-4-(acenaphthene-5-yl) phthalazines is synthetic
In argon atmosphere, 1.20g (4mmol) 1-phenoxy group-4-bromine phthalazines, 0.99g (5mmol) acenaphthene-5-boric acid and 0.28g (0.24mmol) tetra-triphenylphosphine palladium are dissolved in 20mL THF, in reaction system, drip 10mL containing the aqueous solution of 1.38g (10mmol) salt of wormwood subsequently.Heating, stirring reaction 10h under reflux state.After reacting completely, reaction solution is chilled to room temperature naturally, 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 that the volume ratio of take is 1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines 0.67g, yield is 44.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 374.1 (M
+)
Ultimate analysis: C26H18N2O
Theoretical value: C, 83.40; H, 4.85; N, 7.48; O, 4.27;
Measured value: C, 83.46; H, 4.81; N, 7.43; O, 4.30.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines.
(2) main part is the synthesizing containing iridium dichloro dipolymer of 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines
In argon atmosphere, 0.35g (1mmol) three hydration iridous chlorides and 0.94g (2.5mmol) 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines are dissolved in 25mL2-methyl cellosolve, 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, the acetone that the volume ratio of take is 1:15 and the mixed solution of normal hexane are eluent, obtain pure main part and be 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer 0.26g, yield is 26.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1949.4 (M
+)
Ultimate analysis: C104H68Cl2Ir2N8O4
Theoretical value: C, 64.09; H, 3.52; Cl, 3.64; Ir, 19.72; N, 5.75; O, 3.28;
Measured value: C, 64.13; H, 3.45; Cl, 3.68; Ir, 19.70; N, 5.78; O, 3.26.
The resulting material of the above-mentioned reaction of above data acknowledgement be main part be 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines containing iridium dichloro dipolymer.
(3) two [1-phenoxy group-4-(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 the main part of 0.97g (0.5mmol) be 1-phenoxy group-4-(acenaphthene-5-yl) phthalazines 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, 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, the methylene dichloride that the volume ratio of take is 1:22 and the mixed solution of sherwood oil are eluent, steaming desolventizes, dry rear final pure red phosphorescence two [1-phenoxy group-4-(acenaphthene-5-yl) phthalazines-N, the C of obtaining
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.30g, yield is 26.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1124.4 (M
+)
Ultimate analysis: C63H55IrN4O4
Theoretical value: C, 67.30; H, 4.93; Ir, 17.10; N, 4.98; O, 5.69;
Measured value: C, 67.37; H, 4.86; Ir, 17.14; N, 4.95; O, 5.68.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [1-phenoxy group-4-(acenaphthene-5-yl) phthalazines-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 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=0.32.
Embodiment 5
An 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, by vacuum evaporation, preparing successively thickness on anode is 4 of 60nm, 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, N '-bis-(1-naphthyl)-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-methyl-4-(acenaphthene-5-yl) phthalazines-N of the red phosphorescent of embodiment 1 preparation, C
2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium, luminous material of main part is N, N '-bis-carbazyl-4, and the dopant material forming in 4 '-dipyridyl (CBP), the mass percent that luminous guest materials accounts for luminous material of main part is 8%.On this luminescent layer, vacuum evaporation thickness is 10nm 2 successively again, 9-dimethyl-4, three (oxine) aluminium (Alq that 7-phenylbenzene-phenanthrolene (BCP) layer is 20nm as hole blocking layer, thickness
3) oxine lithium (Liq) layer that is 2nm as electron transfer layer, thickness is as electronic injection buffer layer, finally on electronic injection buffer layer, adopt the metal Al layer that vacuum plating techniques of deposition thickness is 100nm, 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 (Keithley 2400 Sourcemeter), 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 6.8%, and maximum lumen efficiency is 5.9lm/W.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a red phosphorescent iridium metal complex, is characterized in that, structural formula is as follows:
Wherein ,-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20.
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 4:4.8～5,1-R-4-bromine phthalazines 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 ligand 1-R-4-(acenaphthene-5-yl) phthalazines, wherein, described-R is that general formula is-C
nh
2n+1alkyl, general formula be-OC
nh
2n+1alkoxyl group, phenyl or phenoxy group, the integer that n is 1～20;
In the second atmosphere of inert gases, be that 2.5～3:1 is dissolved in described ring master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines 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 main part and be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer;
In the 3rd atmosphere of inert gases, in molar ratio 0.5:1.5～2 by described main part be 1-R-4-(acenaphthene-5-yl) phthalazines containing iridium chlorine bridge dipolymer and 2,2,6,6-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:
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 0.2～0.24:4.8～5.
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 ligand 1-R-4-(acenaphthene-5-yl) phthalazines, 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, the methylene dichloride that the volume ratio of take is 1:3～1:10 and the mixed solution of sherwood oil are eluent, steaming desolventizes, after dry, obtain pure ring master metal ligand 1-R-4-(acenaphthene-5-yl) phthalazines.
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 that the volume ratio of take is 1:5～1:15 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, the methylene dichloride that the volume ratio of take is 1:10～1:22 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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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474826A (en) * | 2000-11-30 | 2004-02-11 | ������������ʽ���� | Luminescent element and display |
| US20040142208A1 (en) * | 2001-02-14 | 2004-07-22 | Yuji Hamada | Organic electroluminescence device luminescent material, and organic compound |
| CN102180909A (en) * | 2011-03-18 | 2011-09-14 | 南京邮电大学 | Iridium complex phosphor material taking phthalazine derivative as ligand and preparation method thereof |
| CN102226083A (en) * | 2011-04-22 | 2011-10-26 | 南京邮电大学 | Iridium complex phosphorescent materials with wavelengths from infrared to near-infrared range and preparation method thereof |
| CN102408450A (en) * | 2011-09-23 | 2012-04-11 | 安徽工业大学 | Preparation method of iridium complex-containing phosphorescence material and its application in cobalt ion detection |
| CN102633839A (en) * | 2012-04-11 | 2012-08-15 | 桂林理工大学 | Electrophosphorescent acenaphthene derivative metallic iridium complex |
-
2013
- 2013-05-22 CN CN201310194951.2A patent/CN104178114A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474826A (en) * | 2000-11-30 | 2004-02-11 | ������������ʽ���� | Luminescent element and display |
| US20040142208A1 (en) * | 2001-02-14 | 2004-07-22 | Yuji Hamada | Organic electroluminescence device luminescent material, and organic compound |
| CN102180909A (en) * | 2011-03-18 | 2011-09-14 | 南京邮电大学 | Iridium complex phosphor material taking phthalazine derivative as ligand and preparation method thereof |
| CN102226083A (en) * | 2011-04-22 | 2011-10-26 | 南京邮电大学 | Iridium complex phosphorescent materials with wavelengths from infrared to near-infrared range and preparation method thereof |
| CN102408450A (en) * | 2011-09-23 | 2012-04-11 | 安徽工业大学 | Preparation method of iridium complex-containing phosphorescence material and its application in cobalt ion detection |
| CN102633839A (en) * | 2012-04-11 | 2012-08-15 | 桂林理工大学 | Electrophosphorescent acenaphthene derivative metallic iridium complex |
Non-Patent Citations (1)
| Title |
|---|
| 丁国华等: "苊衍生物铱配合物的合成及发光性能", 《桂林工学院学报》 * |
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Application publication date: 20141203 |