CN104177445A - Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device - Google Patents
Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device Download PDFInfo
- Publication number
- CN104177445A CN104177445A CN201310192657.8A CN201310192657A CN104177445A CN 104177445 A CN104177445 A CN 104177445A CN 201310192657 A CN201310192657 A CN 201310192657A CN 104177445 A CN104177445 A CN 104177445A
- Authority
- CN
- China
- Prior art keywords
- metal complex
- blue phosphorescent
- iridium metal
- reaction
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a blue phosphorescence iridium metal complex, its preparation method and an organic electroluminescent device. The structural formula of the blue phosphorescence iridium metal complex is as defined in the specification, wherein R is hydrogen or an alkyl group with carbon atom number being 1-20. According to the above blue phosphorescence iridium metal complex, 2-(2',4'-difluorophenyl)pyrimidine is used as a cyclometallated ligand main-structure, and tetra(1-pyrazole)boron is used as an auxiliary ligand. With the introduction of two F groups at 4,6- sites of benzene ring of 2-(2',4'-difluorophenyl)pyrimidine and a high-field-intensity auxiliary ligand tetra(1-pyrazole)boron, blue shift of emission wavelength can be realized effectively, and blue ray with high color purity can be emitted. In addition, luminescence property also can be improved. With the application of the blue phosphorescence iridium metal complex in the organic electroluminescent device, luminescence property of the organic electroluminescent device can be raised.
Description
Technical field
The present invention relates to electroluminescent material technical field, particularly relate to a kind of blue phosphorescent iridium metal complex, its preparation method and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, make low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
In order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Compare with green light material with ruddiness, the development of blue light material lags behind comparatively speaking, the efficiency that improves blue light material has just become the breakthrough point of people's researchs with purity of color, but at present there is bottleneck problem at aspects such as the efficiency decay of illuminant colour purity, luminous efficiency and device in blue phosphorescent material always, makes the luminescent properties of organic electroluminescence device poor.Therefore, develop the blue phosphorescent organic electroluminescent material that can improve organic electroluminescence device luminescent properties and become a megatrend of expanding blue light material research field.
Summary of the invention
Based on this, be necessary to provide a kind of blue phosphorescent iridium metal complex that can improve organic electroluminescence device luminescent properties.
A kind of blue phosphorescent iridium metal complex, structural formula is as follows:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Individual in an embodiment therein, described blue phosphorescent iridium metal complex is:
A preparation method for blue phosphorescent iridium metal complex, comprises the steps:
In the first shielding gas atmosphere, for 1:1～1:2 by structural formula be in molar ratio
pyrimidine derivatives and 2,4 difluorobenzene boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8～15 hours, after separation and purification, obtain encircling master metal part, wherein, described R is the alkyl that hydrogen or carbonatoms are 1～20;
In the second shielding gas atmosphere, be that 2～3:1 is dissolved in described ring master metal part and three hydration iridous chlorides in the second solvent in molar ratio, be heated to reflux state reaction 24 hours, after separation and purification, obtain structural formula and be
containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere, the described methanol solution containing iridium chlorine bridge dipolymer and trifluoroacetic acid silver is dissolved in the 3rd solvent, stirring reaction 2～3 hours, centrifugal, get supernatant liquor, revolve steaming and obtain residue except after desolventizing, described residue and four (1-pyrazoles) boronation potassium is dissolved in the 4th solvent, back flow reaction 22～25 hours, obtains blue phosphorescent iridium metal complex after separation and purification; Wherein, the described mol ratio containing iridium chlorine bridge dipolymer and trifluoroacetic acid silver is 1:2.1～2.5, and the described mol ratio containing iridium chlorine bridge dipolymer and four (1-pyrazoles) boronation potassium is 1:2.4～3, and the structural formula of described blue phosphorescent iridium metal complex is:
In an embodiment, described the first solvent is tetrahydrofuran (THF), toluene or dimethyl formamide therein; Described the second solvent is cellosolvo and the water mixed solution that 3:1 mixes by volume; Described the 3rd solvent is methylene dichloride; Described the 4th solvent is acetonitrile.
In an embodiment, described catalyzer is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium therein.
In an embodiment, the molar weight of described catalyzer is that described structural formula is therein
pyrimidine derivatives molar weight 3～6%, the molar weight of the carbonate in the aqueous solution of described carbonate is that described structural formula is
1～4 times of molar weight of pyrimidine derivatives.
Therein in an embodiment, after described separation and purification, obtain encircling in the step of master metal part, the method for separation and purification is specially: reaction finishes, and question response liquid cooling is to room temperature, dichloromethane extraction, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, described crude product is carried out to silica gel column chromatography separation, after being dried, must encircle master metal part.
Therein in an embodiment, after described separation and purification, obtain structural formula and be
containing in the step of iridium chlorine bridge dipolymer, the method for separation and purification is specially: reaction finishes, and reaction solution is chilled to after room temperature, rotation is steamed except partial solvent, adds distilled water, filters, solid is used distilled water, methanol wash successively, obtains structural formula after dry to be
containing iridium chlorine bridge dipolymer.
Therein in an embodiment, after described separation and purification, obtain in the step of blue phosphorescent iridium metal complex, the method of separation and purification is specially: reaction finishes, and reaction solution is chilled to after room temperature naturally, filters, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, and obtains crude product, described crude product is used methyl alcohol, deionized water wash successively, then the crude product after to washing carries out recrystallization and obtains blue phosphorescent iridium metal complex with methyl alcohol and methylene dichloride mixed solution.
A kind of organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, electronic barrier 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 blue phosphorescent iridium metal complex.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2', 4'-difluorophenyl) pyrimidine is cyclic metal complexes agent structure, taking four (1-pyrazoles) change boron as assistant ligand, 2-(2', 4'-difluorophenyl) on the phenyl ring of pyrimidine 4, two F bases of 6-position and high field intensity assistant ligand four (1-pyrazoles) are changed the introducing blue shift emission wavelength effectively of boron, can launch the blue light of high color purity, can also improve luminescent properties.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, can improves the luminescent properties of organic electroluminescence device.
Brief description of the drawings
Fig. 1 is the preparation method's of the blue phosphorescent iridium metal complex of an embodiment schema;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, C prepared by embodiment 1
2') (four (1-pyrazoles) change boron) close the utilizing emitted light spectrogram of complex of iridium.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The blue phosphorescent iridium metal complex of one embodiment, structural formula is as follows:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Carbonatoms is that 1～20 alkyl can straight chained alkyl or branched-chain alkyl.
When R is carbonatoms while being 1～20 alkyl, the hydrogen on 4-position or the 5-position of R substituted pyrimidines, the structural formula of this blue phosphorescent iridium metal complex is:
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2', 4'-difluorophenyl) pyrimidine is cyclic metal complexes agent structure, taking four (1-pyrazoles) change boron as assistant ligand, 2-(2 ', 4 '-difluorophenyl) on the phenyl ring of pyrimidine 4, two F bases of 6-position and high field intensity assistant ligand four (1-pyrazoles) are changed the introducing blue shift emission wavelength effectively of boron, can launch the blue light of high color purity, obtain satisfied blue light, can also improve luminescent properties.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, can improves the luminescent properties of organic electroluminescence device.
And, alkyl is introduced in pyrimidine ring and can be obtained more satisfied energy transmission efficiency and blue light emitting wavelength, not only be conducive to increase its solvability in organic solvent, and produce certain space steric effect, thereby the direct effect between minimizing atoms metal, the self-quenching phenomenon that reduces triplet exciton, obtains stronger phosphorescent emissions, further improves the luminescent properties of organic electroluminescence device.Meanwhile, the introducing of alkyl is beneficial to evaporation, increases the stability of the luminescent device of film-forming properties this blue phosphorescent iridium metal complex of raising use.
Refer to Fig. 1, the preparation method of the blue phosphorescent iridium metal complex of an embodiment, comprises the steps S110～S130.
Step S110: in the first shielding gas atmosphere, for 1:1～1:2 by structural formula be in molar ratio
pyrimidine derivatives and 2,4 difluorobenzene boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8～15 hours, after separation and purification, obtain encircling master metal part, wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Pyrimidine derivatives
in R be the alkyl that hydrogen or carbonatoms are 1～20.Carbonatoms is that 1～20 alkyl can straight chained alkyl or branched-chain alkyl.When R is carbonatoms while being 1～20 alkyl, the hydrogen on 4-position or the 5-position of R substituted pyrimidines.
The first shielding gas is nitrogen, argon gas, helium or neon.
The first solvent is tetrahydrofuran (THF) (THF), toluene or dimethyl formamide (DMF).Structural formula is
pyrimidine derivatives concentration in the first solvent be 0.17～0.33mol/L.
Catalyzer is palladium catalyst, is preferably four (triphenyl phosphorus) and closes palladium (Pd (PP
3)
4) or two chlorine two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2).
Preferably, catalyzer molar weight is that structural formula is
pyrimidine derivatives molar weight 3%～6%.
The aqueous solution of carbonate is the aqueous solution of sodium carbonate or salt of wormwood.The volumetric molar concentration of the aqueous solution of carbonate is 0.8～1.25mmol/mL.The molar weight of the carbonate in the aqueous solution of carbonate and structural formula are
1～4 times of molar weight of pyrimidine derivatives.
For 1:1～1:2, pyrimidine derivatives and 2,4 difluorobenzene boric acid are dissolved in the first solvent in molar ratio, add the aqueous solution of catalyzer and carbonate, heating, under reflux state, stir 8～15 hours, carry out Suzuki linked reaction, after separation and purification, obtain encircling master metal part.The reaction formula of above-mentioned Suzuki linked reaction is as follows:
Ring master metal part
in, R is the alkyl that hydrogen or carbonatoms are 1～20.When R is carbonatoms while being 1～20 alkyl, the hydrogen on 4-position or the 5-position of R substituted pyrimidines.
Ring master metal part is specifically as follows 2-(2', 4'-difluorophenyl) pyrimidine, 2-(2', 4'-difluorophenyl)-5-methylpyrimidine, 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine, 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine etc.
The method of separation and purification is specially: reaction finishes, question response liquid cooling is to room temperature, dichloromethane extraction, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, after being dried, must encircle master metal part.
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 shielding gas atmosphere, be that 2～3:1 is dissolved in ring master metal part and three hydration iridous chlorides in the second solvent in molar ratio, be heated to reflux state reaction 24 hours, obtain after separation and purification containing iridium chlorine bridge dipolymer.
Structural formula containing iridium chlorine bridge dipolymer is
r in structural formula is the alkyl that hydrogen or carbonatoms are 1～20.Carbonatoms is that 1～20 alkyl can straight chained alkyl or branched-chain alkyl.When R is carbonatoms while being 1～20 alkyl, the hydrogen on 4-position or the 5-position of R substituted pyrimidines.For example, can be 2-(2' for part containing iridium chlorine bridge dipolymer, 4'-difluorophenyl) pyrimidine be 2-(2' containing iridium dichloro dipolymer, part, 4'-difluorophenyl)-5-methylpyrimidine be 2-(2' containing iridium dichloro dipolymer, part, 4'-difluorophenyl)-5-tertiary butyl pyrimidine containing iridium dichloro dipolymer, part be 2-(2', 4'-difluorophenyl)-4-eicosyl yl pyrimidines containing iridium dichloro dipolymer etc.
The second shielding gas is nitrogen, argon gas, helium or neon.
The second solvent is cellosolvo and the water mixed solution that 3:1 mixes by volume.The concentration of ring master metal part in the second solvent is 0.05～0.125mmol/L.
Be that 2～3:1 will encircle master metal part and three hydration iridous chloride (IrCl in molar ratio
33H
2o) be dissolved in the second solvent, be heated to reflux state reaction 24 hours, after separation and purification, obtain structural formula and be
containing iridium chlorine bridge dipolymer, reaction formula is as follows:
The method of separation and purification is specially: reaction end, and reaction solution is chilled to after room temperature, and rotation is steamed except partial solvent, adds distilled water, filters, and solid is used distilled water, methanol wash successively, after being dried, obtains 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 shielding gas atmosphere; to be dissolved in the 3rd solvent containing the methanol solution of iridium chlorine bridge dipolymer and trifluoroacetic acid silver; stirring reaction 2～3 hours; centrifugal; get supernatant liquor, revolve steaming and obtain residue except after desolventizing, residue and four (1-pyrazoles) boronation potassium is dissolved in the 4th solvent; back flow reaction 22～25 hours, obtains blue phosphorescent iridium metal complex after separation and purification.
The 3rd shielding gas is nitrogen, argon gas, helium or neon.
The concentration of the methanol solution of trifluoroacetic acid silver is 0.042～0.055mmol/mL.Mol ratio containing the trifluoroacetic acid silver in the methanol solution of iridium chlorine bridge dipolymer and trifluoroacetic acid silver is 1:2.1～2.5.
The 3rd solvent is methylene dichloride.Solid-to-liquid ratio containing iridium chlorine bridge dipolymer and the 3rd solvent is 0.72～1.44g:30～50mL.
The 4th solvent is acetonitrile.The solid-to-liquid ratio of four (1-pyrazoles) boronation potassium and the 4th solvent is 0.38～0.95g:20～30mL.
In the 3rd shielding gas atmosphere; to be dissolved in the 3rd solvent containing iridium chlorine bridge dipolymer; at room temperature drip the methanol solution of trifluoroacetic acid silver; dropwise rear stirring reaction 2～3 hours, centrifugal, get supernatant liquor; revolve to steam except after desolventizing and obtain residue; residue and four (1-pyrazoles) boronation potassium is dissolved in the 4th solvent, and back flow reaction 22～25 hours, obtains blue phosphorescent iridium metal complex after separation and purification.Net reaction is as follows:
React with trifluoroacetic acid silver containing iridium chlorine bridge dipolymer, generate silver nitride precipitation, avoid containing the chloride ion interference reaction in iridium chlorine bridge dipolymer.
The method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature naturally, filter, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, and obtains crude product, described crude product is used methyl alcohol, deionized water wash successively, then the crude product after to washing carries out recrystallization and obtains blue phosphorescent iridium metal complex with methyl alcohol and methylene dichloride mixed solution.
The structural formula of blue phosphorescent iridium metal complex is:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Carbonatoms is that 1～20 alkyl can straight chained alkyl or branched-chain alkyl.When R is carbonatoms while being 1～20 alkyl, the hydrogen on 4-position or the 5-position of R substituted pyrimidines.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Preparation method's reaction conditions gentleness of above-mentioned blue phosphorescent iridium metal complex, lower to equipment requirements, preparation cost is low, is easy to extensive preparation.
Refer to Fig. 2, the organic electroluminescence device 300 of one embodiment, comprises the substrate 301, anode 302, hole injection layer 303, hole transmission layer 304, electronic barrier layer 305, luminescent layer 306, hole blocking layer 307, electron transfer layer 308, electronic injection buffer layer 309 and the negative electrode 310 that stack gradually.
The material of substrate 301, anode 302, hole injection layer 303, hole transmission layer 304, electronic barrier layer 305, hole blocking layer 307, electron transfer layer 308, electronic injection buffer layer 309 and negative electrode 310 is respectively the common used material of this area.For example, substrate 101 is glass substrate, the material of anode 302 is tin indium oxide (ITO), the material of hole injection layer 303 is 4, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), the material of hole transmission layer 304 is N, two (1-the naphthyl)-N of N'-, N '-phenylbenzene benzidine (NPB), the material of electronic barrier layer 305 is 1, two (9-carbazyl) benzene (mCP) of 3-, the material of hole blocking layer 307 is 2, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene (BCP), the material of electron transfer layer 308 is three (oxine) aluminium (Alq
3), the material of electronic injection buffer layer 309 is that the material of lithium fluoride (LiF), 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 blue phosphorescent iridium metal complex, and luminous material of main part is two (9-carbazyl) benzene (mCP) of 1,3-.The mass percent that luminous guest materials accounts for luminous material of main part is 7%.
Above-mentioned blue phosphorescent iridium metal complex and luminous material of main part have good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device 300 is due to the blue phosphorescent iridium metal complex that contains high color purity in luminescent layer 306, thereby can launch high purity blue light, and this blue 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
Blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-difluorophenyl) pyrimidine is synthetic
In nitrogen atmosphere, by 1.59g (10mmol) 2-bromo pyrimi piperidine, 1.90g (12mmol) 2,4-difluorobenzene boric acid and 0.69g (0.6mmol) four (triphenyl phosphorus) closes palladium and is dissolved in 30mL toluene, drips the aqueous solution of 20mL containing 3.31g (24mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 8h under reflux state.Reaction finishes, question response liquid cooling is to room temperature, and dichloromethane extraction, gets organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, after dry, obtain 2-(2', 4'-difluorophenyl) pyrimidine 1.21g, yield is 63.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 192.0 (M
+)
Ultimate analysis: C
10h
6f
2n
2
Theoretical value: C, 62.50; H, 3.15; F, 19.77; N, 14.58;
Measured value: C, 62.56; H, 3.10; F, 19.72; N, 14.62.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-difluorophenyl) pyrimidine.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-difluorophenyl) pyrimidine
In nitrogen atmosphere, by 0.36g (1mmol) three hydration iridous chlorides and 0.48g (2.5mmol) 2-(2', 4'-difluorophenyl) pyrimidine is dissolved in 25mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 24h under reflux state.Reaction finishes, and reaction solution is chilled to after room temperature, and rotation is steamed except partial solvent, add appropriate distilled water, filter, solid is used distilled water, methanol wash successively, after dry, obtain part and be 2-(2', 4'-difluorophenyl) pyrimidine containing iridium dichloro dipolymer 0.38g, yield is 62.3%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-difluorophenyl) pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium
In nitrogen atmosphere, be 2-(2' by the main part of 1.22g (1mmol), 4'-difluorophenyl) being dissolved in 50mL methylene dichloride containing iridium dichloro dipolymer of pyrimidine, at room temperature drip subsequently the methanol solution of 50mL containing 0.46g (2.1mmol) trifluoroacetic acid silver, dropwise rear stirring reaction 2h.With whizzer, reaction solution is carried out centrifugally, remove AgCl precipitation, get supernatant liquor, rotation is steamed and is desolventized, and obtains residue.In nitrogen atmosphere, residue and 0.95g (3mmol) four (1-pyrazoles) boronation potassium are dissolved in 30mL acetonitrile to back flow reaction 24h.Reaction finishes, reaction solution is chilled to room temperature, filter, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, obtain crude product, crude product is used methyl alcohol, deionized water wash successively, then obtains the two (2-(4' of blue phosphorescent with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-difluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.43g, productive rate is 25.2%.
Net reaction is as follows:
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M
+)
Ultimate analysis: C32H22BF4IrN12
Theoretical value: C, 45.03; H, 2.60; B, 1.27; F, 8.90; Ir, 22.52; N, 19.69;
Measured value: C, 45.07; H, 2.53; B, 1.29; F, 8.95; Ir, 22.50; N, 19.66.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-difluorophenyl) pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close complex of iridium.
As shown in Figure 3, transverse axis is wavelength (Wavelength, the nm of unit), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), and end product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M), at 458nm place, has an acromion at 486nm place simultaneously, and blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, C are described
2') (four (1-pyrazoles) change boron) to close the purity of color of complex of iridium higher, this can be used as blue light electroluminescent material and is widely used in the preparation field of organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, taking concentration as～10
-6the CH of the FIrpic of M
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.24, blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, the C of visible the present embodiment
2') (four (1-pyrazoles) change boron) close complex of iridium and have higher luminous quantum efficiency.
Embodiment 2
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-difluorophenyl)-5-methylpyrimidine is synthetic
In argon atmosphere, by the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 1.58g (10mmol) 2,4-difluorobenzene boric acid and 0.35g (0.5mmol) dichloro two (triphenyl phosphorus) closes palladium and is dissolved in 60mL DMF, drips the aqueous solution of 40mL containing 3.18g (30mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 90 DEG C of state of temperatures.Reaction finishes, question response liquid cooling is to room temperature, dichloromethane extraction, is washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, after being dried, obtains 2-(2', 4'-difluorophenyl)-5-methylpyrimidine 1.24g, yield is 59.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 206.1 (M
+)
Ultimate analysis: C11H8F2N2
Theoretical value: C, 64.08; H, 3.91; F, 18.43; N, 13.59;
Measured value: C, 64.14; H, 3.88; F, 18.36; N, 13.62.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-difluorophenyl)-5-methylpyrimidine.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-difluorophenyl)-5-methylpyrimidine
In argon atmosphere, by 0.70g (2mmol) three hydration iridous chlorides and 1.24g (6mmol) 2-(2', 4'-difluorophenyl)-5-methylpyrimidine is dissolved in 50mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 24h under reflux state.Reaction finishes, and reaction solution is chilled to after room temperature, and rotation is steamed except partial solvent, add appropriate distilled water, filter, solid is used distilled water, methanol wash successively, after dry, obtain part and be 2-(2', 4'-difluorophenyl)-5-methylpyrimidine containing iridium dichloro dipolymer 0.69g, yield is 54.1%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium
In argon atmosphere, be 2-(2' by the main part of 1.28g (1mmol), 4'-difluorophenyl) being dissolved in 50mL methylene dichloride containing iridium dichloro dipolymer of-5-methylpyrimidine, at room temperature drip subsequently the methanol solution of 50mL containing 0.48g (2.2mmol) trifluoroacetic acid silver, dropwise rear stirring reaction 3h.With whizzer, reaction solution is carried out centrifugally, remove AgCl precipitation, get supernatant liquor, rotation is steamed and is desolventized, and obtains residue.In nitrogen protection atmosphere, residue and 0.80g (2.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 30mL acetonitrile to back flow reaction 22h.Reaction finishes, reaction solution is chilled to room temperature, filter, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, obtain crude product, crude product is used methyl alcohol, deionized water wash successively, then obtains the two (2-(4' of blue phosphorescent with methyl alcohol and methylene dichloride mixed solution recrystallization, 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.39g, productive rate is 22.1%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 882.2 (M
+)
Ultimate analysis: C34H26BF4IrN12
Theoretical value: C, 46.32; H, 2.97; B, 1.23; F, 8.62; Ir, 21.80; N, 19.06;
Measured value: C, 46.36; H, 2.92; B, 1.27; F, 8.64; Ir, 21.72; N, 19.09.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 457nm place, has an acromion at 485nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.15, blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, the C of visible the present embodiment
2') (four (1-pyrazoles) change boron) close complex of iridium and have higher luminous quantum efficiency, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
Embodiment 3
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine is synthetic
In neon atmosphere, by the bromo-5-tertiary butyl of 2.15g (10mmol) 2-pyrimidine, 2.53g (16mmol) 2,4-difluorobenzene boric acid and 0.35g (0.30mmol) four (triphenyl phosphorus) closes palladium and is dissolved in 50mL DMF, drips the aqueous solution of 20mL containing 4.24g (40mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.Reaction finishes, question response liquid cooling is to room temperature, dichloromethane extraction, is washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, after being dried, obtains 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine 0.99g, yield is 39.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 248.1 (M
+)
Ultimate analysis: C14H14F2N2
Theoretical value: C, 67.73; H, 5.68; F, 15.30; N, 11.28;
Measured value: C, 67.66; H, 5.75; F, 15.37; N, 11.22.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine
In neon atmosphere, by 0.70g (2mmol) three hydration iridous chlorides and 1.24g (5mmol) 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine is dissolved in 40mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 24h under reflux state.Reaction finishes, reaction solution is chilled to after room temperature, rotation is steamed except partial solvent, add appropriate distilled water, filter, solid is used distilled water, methanol wash successively, and after being dried, obtaining part is 2-(2', 4'-difluorophenyl)-5-tertiary butyl pyrimidine containing iridium dichloro dipolymer 0.58g, yield is 40.2%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close complex of iridium
In neon atmosphere, be 2-(2' by the main part of 1.44g (1mmol), 4'-difluorophenyl) being dissolved in 50mL methylene dichloride containing iridium dichloro dipolymer of-5-tertiary butyl pyrimidine, at room temperature drip subsequently the methanol solution of 50mL containing 0.55g (2.5mmol) trifluoroacetic acid silver, dropwise rear stirring reaction 3h.With whizzer, reaction solution is carried out centrifugally, remove AgCl precipitation, get supernatant liquor, rotation is steamed and is desolventized, and obtains residue.In nitrogen protection atmosphere, residue and 0.80g (2.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 30mL acetonitrile to back flow reaction 25h.Reaction finishes, reaction solution is chilled to room temperature, filter, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, obtain crude product, crude product is used methyl alcohol, deionized water wash successively, then obtains the two (2-(4' of blue phosphorescent with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.39g, productive rate is 20.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 966.3 (M
+)
Ultimate analysis: C40H38BF4IrN12
Theoretical value: C, 49.74; H, 3.97; B, 1.12; F, 7.87; Ir, 19.90; N, 17.40;
Measured value: C, 49.71; H, 3.95; B, 1.18; F, 7.84; Ir, 19.95; N, 17.37.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 464nm place, has an acromion at 492nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.25.
Embodiment 4
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine is synthetic
In nitrogen atmosphere, by the bromo-4-eicosyl of 2.20g (5mmol) 2-pyrimidine, 1.58g (10mmol) 2,4-difluorobenzene boric acid and 0.21g (0.30mmol) dichloro two (triphenyl phosphorus) closes and is dissolved in 30mL toluene, drips the aqueous solution of 20mL containing 1.38g (10mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 10h under reflux state.Reaction finishes, question response liquid cooling is to room temperature, dichloromethane extraction, is washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, after being dried, obtains 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine 0.50g, yield is 21.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 472.4 (M
+)
Ultimate analysis: C30H46F2N2
Theoretical value: C, 76.23; H, 9.81; F, 8.04; N, 5.93;
Measured value: C, 76.25; H, 9.75; F, 8.09; N, 5.91.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-difluorophenyl)-4-eicosyl yl pyrimidines
In nitrogen atmosphere, by 0.35g (1mmol) three hydration iridous chlorides and 0.94g (2mmol) 2-(2', 4'-difluorophenyl)-4 eicosyl pyrimidines are dissolved in 40mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 24h under reflux state.Reaction finishes, reaction solution is chilled to after room temperature, rotation is steamed except partial solvent, add appropriate distilled water, filter, solid is used distilled water, methanol wash successively, and after being dried, obtaining part is 2-(2', 4'-difluorophenyl)-4-eicosyl yl pyrimidines containing iridium dichloro dipolymer 0.42g, yield is 17.9%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium
In nitrogen atmosphere, be 2-(2' by the main part of 0.72g (0.5mmol), 4'-difluorophenyl) being dissolved in 30mL methylene dichloride containing iridium dichloro dimer of-4-tertiary butyl pyrimidine, at room temperature drip subsequently the methanol solution of 20mL containing 0.24g (1.1mmol) trifluoroacetic acid silver, dropwise rear stirring reaction 3h.With whizzer, reaction solution is carried out centrifugally, remove AgCl precipitation, get supernatant liquor, rotation is steamed and is desolventized, and obtains residue.In nitrogen protection atmosphere, residue and 0.38g (1.2mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile to back flow reaction 24h.Reaction finishes, reaction solution is chilled to room temperature, filter filter residue washed with dichloromethane, merging filtrate, rotation is steamed and is desolventized, crude product, crude product is used methyl alcohol, deionized water wash successively, then obtains blue phosphorescent couple (2-(4' with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.14g, productive rate is 12.3%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1414.8 (M
+)
Ultimate analysis: C72H102BF4IrN12
Theoretical value: C, 61.13; H, 7.27; B, 0.76; F, 5.37; Ir, 13.59; N, 11.88;
Measured value: C, 61.17; H, 7.21; B, 0.79; F, 5.33; Ir, 13.56; N, 11.94.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 478nm place, has an acromion at 507nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.12.
Embodiment 5
A kind of organic electroluminescence device, comprises the substrate, anode, hole injection layer, hole transmission layer, electronic barrier 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 200nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as anode, on anode, preparing successively thickness by vacuum evaporation is 4 of 40nm, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) layer is as hole injection layer, thickness is the N of 20nm, two (1-the naphthyl)-N of N'-, N'-phenylbenzene benzidine (NPB) layer is as hole transmission layer, thickness is 1 of 10nm, the luminescent layer that two (9-carbazyl) benzene (mCP) layers of 3-are 30nm as electronic barrier 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 the two (2-(4' of blue phosphorescent prepared by embodiment 1, 6'-difluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium, luminous material of main part is two (9-carbazyl) benzene (mCP) of 1,3-, the mass percent that luminous guest materials accounts for luminous material of main part is 7%.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 35nm as hole blocking layer, thickness
3) lithium fluoride (LiF) layer that is 1nm 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 120nm, as the negative electrode of organic electroluminescence device, obtain organic electroluminescence device, representation is ITO (200nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%Ir title complex (30nm)/BCP (10nm)/Alq
3(35nm)/LiF (1nm)/Al (120nm).
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency that records organic electroluminescence device is 8.8%, and maximum lumen efficiency is 12.8lm/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 (10)
1. a blue phosphorescent iridium metal complex, is characterized in that, structural formula is as follows:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
2. blue phosphorescent iridium metal complex according to claim 1, is characterized in that, described blue phosphorescent iridium metal complex is:
3. a preparation method for blue phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In the first shielding gas atmosphere, for 1:1～1:2 by structural formula be in molar ratio
pyrimidine derivatives and 2,4 difluorobenzene boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8～15 hours, after separation and purification, obtain encircling master metal part, wherein, described R is the alkyl that hydrogen or carbonatoms are 1～20;
In the second shielding gas atmosphere, for 2:1～3:1, described ring master metal part and three hydration iridous chlorides are dissolved in the second solvent in molar ratio, be heated to reflux state reaction 24 hours, after separation and purification, obtain structural formula and be
containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere, the described methanol solution containing iridium chlorine bridge dipolymer and trifluoroacetic acid silver is dissolved in the 3rd solvent, stirring reaction 2～3 hours, centrifugal, get supernatant liquor, revolve steaming and obtain residue except after desolventizing, described residue and four (1-pyrazoles) boronation potassium is dissolved in the 4th solvent, back flow reaction 22～25 hours, obtains blue phosphorescent iridium metal complex after separation and purification; Wherein, the described mol ratio containing iridium chlorine bridge dipolymer and trifluoroacetic acid silver is 1:2.1～2.5, and the described mol ratio containing iridium chlorine bridge dipolymer and four (1-pyrazoles) boronation potassium is 1:2.4～3, and the structural formula of described blue phosphorescent iridium metal complex is:
4. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, described the first solvent is tetrahydrofuran (THF), toluene or dimethyl formamide; Described the second solvent is cellosolvo and the water mixed solution that 3:1 mixes by volume; Described the 3rd solvent is methylene dichloride; Described the 4th solvent is acetonitrile.
5. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, described catalyzer is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium.
6. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, the molar weight of described catalyzer is that described structural formula is
pyrimidine derivatives molar weight 3～6%, the molar weight of the carbonate in the aqueous solution of described carbonate is that described structural formula is
1～4 times of molar weight of pyrimidine derivatives.
7. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, after described separation and purification, obtain encircling in the step of master metal part, the method of separation and purification is specially: reaction finishes, question response liquid cooling is to room temperature, dichloromethane extraction, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, taking methylene dichloride as elutriant, described crude product is carried out to silica gel column chromatography separation, after being dried, must encircle master metal part.
8. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, obtains structural formula to be after described separation and purification
containing in the step of iridium chlorine bridge dipolymer, the method for separation and purification is specially: reaction finishes, and reaction solution is chilled to after room temperature, rotation is steamed except partial solvent, adds distilled water, filters, solid is used distilled water, methanol wash successively, obtains structural formula after dry to be
containing iridium chlorine bridge dipolymer.
9. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, after described separation and purification, obtain in the step of blue phosphorescent iridium metal complex, the method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature naturally, filter, filter residue with washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, obtain crude product, described crude product is used methyl alcohol, deionized water wash successively, then with methyl alcohol and methylene dichloride by the crude product of mixed solution after to washing carry out recrystallization and obtain blue phosphorescent iridium metal complex.
10. an organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, electronic barrier 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 the blue phosphorescent iridium metal complex described in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192657.8A CN104177445A (en) | 2013-05-22 | 2013-05-22 | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192657.8A CN104177445A (en) | 2013-05-22 | 2013-05-22 | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104177445A true CN104177445A (en) | 2014-12-03 |
Family
ID=51958818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310192657.8A Pending CN104177445A (en) | 2013-05-22 | 2013-05-22 | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177445A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685358A (en) * | 2020-12-30 | 2022-07-01 | 中国科学院福建物质结构研究所 | Fluorine-containing organic blue light material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120208999A1 (en) * | 2009-08-27 | 2012-08-16 | National Institute Of Advanced Industrial Science And Technology | Iridium complex and light emitting material formed from same |
| CN103003358A (en) * | 2010-07-16 | 2013-03-27 | 住友化学株式会社 | Composition containing polymer compound and light-emitting element using same |
-
2013
- 2013-05-22 CN CN201310192657.8A patent/CN104177445A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120208999A1 (en) * | 2009-08-27 | 2012-08-16 | National Institute Of Advanced Industrial Science And Technology | Iridium complex and light emitting material formed from same |
| CN103003358A (en) * | 2010-07-16 | 2013-03-27 | 住友化学株式会社 | Composition containing polymer compound and light-emitting element using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685358A (en) * | 2020-12-30 | 2022-07-01 | 中国科学院福建物质结构研究所 | Fluorine-containing organic blue light material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104177445A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177436A (en) | Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device | |
| CN104178107A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177414A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177426A (en) | Blue phosphorescence iridium metal complex, preparation method thereof, and organic electroluminescent device | |
| CN104177419A (en) | Blue phosphorescence material iridium metal complex, preparation method and organic electroluminescent device | |
| CN104327123A (en) | Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device | |
| CN104177434A (en) | Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device | |
| CN104178106A (en) | Red phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177432A (en) | Blue-light organic electrophosphorescent materials, preparing method thereof and applications of the materials | |
| CN104177431A (en) | Phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device | |
| CN103965872A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN103965251A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN104178112A (en) | Blue phosphorescence iridium metal complex, preparation method thereof, and organic electroluminescent device | |
| CN104177417A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN103965875A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN104177428A (en) | Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent devices | |
| CN104177411A (en) | Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device | |
| CN104178108A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177420A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177438A (en) | Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device | |
| CN104177437A (en) | Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device | |
| CN104177418A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device | |
| CN104177444A (en) | Blue phosphorescence material iridium metal complex, preparation method and organic electroluminescent device | |
| CN104178105A (en) | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141203 |