CN104178112A - Blue phosphorescence iridium metal complex, preparation method thereof, and organic electroluminescent device - Google Patents
Blue phosphorescence iridium metal complex, preparation method thereof, and organic electroluminescent device Download PDFInfo
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- 0 Brc1n*ccn1 Chemical compound Brc1n*ccn1 0.000 description 4
- XMWNYOCVYLVHNZ-UHFFFAOYSA-N Bc(c(F)c1)ccc1F Chemical compound Bc(c(F)c1)ccc1F XMWNYOCVYLVHNZ-UHFFFAOYSA-N 0.000 description 2
- IPEJYDSOKWOWDS-UHFFFAOYSA-N Brc1nc(I)ccn1 Chemical compound Brc1nc(I)ccn1 IPEJYDSOKWOWDS-UHFFFAOYSA-N 0.000 description 1
- PGFIHORVILKHIA-UHFFFAOYSA-N Brc1ncccn1 Chemical compound Brc1ncccn1 PGFIHORVILKHIA-UHFFFAOYSA-N 0.000 description 1
- MEFWLFIFTRCTCL-CFHWGYOPSA-N CC(C(C=CC(C1)F)=C1[F]C)/N=C\C(\C)=C/N Chemical compound CC(C(C=CC(C1)F)=C1[F]C)/N=C\C(\C)=C/N MEFWLFIFTRCTCL-CFHWGYOPSA-N 0.000 description 1
- KYCGEJNZMHUBMX-UHFFFAOYSA-N Cc(cn1)cnc1Br Chemical compound Cc(cn1)cnc1Br KYCGEJNZMHUBMX-UHFFFAOYSA-N 0.000 description 1
- BBRHREFRBBVFLZ-UHFFFAOYSA-N Fc(cc1)cc(F)c1-c1ncccn1 Chemical compound Fc(cc1)cc(F)c1-c1ncccn1 BBRHREFRBBVFLZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a blue phosphorescence iridium metal complex, a preparation method thereof, and an organic electroluminescent device. A structural formula of the blue phosphorescence iridium metal complex is shown in the description. In the structural general formula, R represents hydrogen or alkyl of C1-C20. The blue phosphorescence iridium metal complex takes use of 2-(4',6'-difluorophenyl)pyrimidine as a cyclometalated ligand main structure and 2-pyridinecarboxylic acid as auxiliary ligands. By introducing two F groups on 4,6-sites of a benzene ring of 2-(4',6'-difluorophenyl)pyrimidine and high field intensity auxiliary ligands of 2-picolinic acid, not only can luminescent wavelengths shift toward blue effectively, but also high-color purity can be emitted, thereby improving luminescent properties and enhancing luminescent intensity. By applying the blue light phosphorescence iridium metal complex in the organic electroluminescent device, the luminescent properties of the organic electroluminescent device can be improved.
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, 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 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 there is bottleneck problem at the aspects such as efficiency decay of illuminant colour purity, luminous efficiency and device in blue phosphorescent material at present always, make 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 blue phosphorescent iridium metal complex, structural formula is as follows:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
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, 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; 1:2～1:4 is dissolved in the 3rd solvent containing iridium chlorine bridge dipolymer and 2-pyridine carboxylic acid described in molar ratio; be heated to reflux state reaction 8～20 hours; after separation and purification, obtain blue phosphorescent iridium metal complex, 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 cellosolvo or trichlorotoluene zotrichloride.
In an embodiment, described catalyzer is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium therein.
Therein in an embodiment, the molar weight of described catalyzer be described 2,4 difluorobenzene boric acid molar weight 3～6%.
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, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, take methylene dichloride as elutriant carries out silica gel column chromatography separation to described crude product, 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, reaction solution is chilled to after room temperature naturally, adds methyl alcohol after removing partial solvent under reduced pressure, filters, solid is used normal hexane, the ultrasonic lower washing of ether successively, the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to described washing, and steaming desolventizes, and obtains blue phosphorescent iridium metal complex after dry.
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 is doped in the luminous guest materials in described luminous material of main part, the above-mentioned blue phosphorescent iridium metal complex of described luminous guest materials.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(4', 6'-difluorophenyl) pyrimidine is cyclic metal complexes agent structure, take 2-pyridine carboxylic acid as assistant ligand, 2-(4', 6'-difluorophenyl) on the phenyl ring of pyrimidine 4, two F bases of 6-position and the introducing of high field intensity assistant ligand 2-pyridine carboxylic acid be blue shift emission wavelength effectively, can launch the blue light of high color purity, can also improve luminescent properties, improve luminous intensity.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, can improves the luminescent properties of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is preparation method's the schema of the blue phosphorescent iridium metal complex of an embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is two (2-(4', 6'-difluorophenyl) pyrimidine-N, C of the blue phosphorescent of embodiment 1 preparation
2') (2-pyridine formyl) 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.
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 4-position of R substituted pyrimidines or the hydrogen on 5-position.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(4', 6'-difluorophenyl) pyrimidine is cyclic metal complexes agent structure, take 2-pyridine carboxylic acid as assistant ligand, on the phenyl ring of 2-(4', 6'-difluorophenyl) pyrimidine 4, two F bases of 6-position and the introducing of high field intensity assistant ligand 2-pyridine carboxylic acid be blue shift emission wavelength effectively, can there is the blue light of high color purity, obtain satisfied blue light, can also improve luminescent properties, improve luminous intensity.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, can improves the luminescent properties of organic electroluminescence device.
And, when R is that carbonatoms is while being 1～20 alkyl, 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, thus reduce the direct effect between atoms metal, reduce the self-quenching phenomenon of triplet exciton, obtain stronger phosphorescent emissions, further improve the luminescent properties of organic electroluminescence device.Meanwhile, the introducing of alkyl is beneficial to evaporation, increases the stability that the luminescent device of this blue phosphorescent iridium metal complex is used in film-forming properties raising.
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 atom 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 4-position of R substituted pyrimidines or the hydrogen on 5-position.
The first shielding gas is nitrogen, argon gas, helium or neon.
The first solvent is tetrahydrofuran (THF), toluene or dimethyl formamide.The solid-to-liquid ratio of 2,4 difluorobenzene boric acid and the first solvent is 0.95～1.90g:20～40mL.The concentration of 2,4 difluorobenzene boric acid in the first solvent is 0.1～0.2mol/L.
Catalyzer is palladium catalyst, is preferably four (triphenyl phosphorus) and closes palladium (Pd[P (C
6h
5)
3]
4) or two chlorine two (triphenyl phosphorus) close palladium (C
36h
30cl
2p
2pd).
Preferably, the molar weight of catalyzer is 3～6% of 2,4 difluorobenzene boric acid molar weight.
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 0.5～2mmol/mL.The molar weight of the carbonate in the aqueous solution of carbonate is mole make a gesture of measuring 2～4 times of 2,4 difluorobenzene boric acid.
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 85～100 ℃, 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, when R is carbonatoms while being 1～20 alkyl, the 4-position of R substituted pyrimidines or the hydrogen on 5-position.
For example, 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, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, take methylene dichloride as elutriant carries out silica gel column chromatography separation to described crude product, 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, for 2:1～3:1, ring master metal part and three hydration iridous chlorides are dissolved in the second solvent in molar ratio, are 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 4-position of R substituted pyrimidines or the hydrogen on 5-position.For example, containing iridium chlorine bridge dipolymer, can be 2-(2' for part, 4'-difluorophenyl)-4-eicosyl yl pyrimidines containing iridium dichloro dipolymer, part, be 2-(2', 4'-difluorophenyl)-5-methylpyrimidine containing iridium dichloro dipolymer, part, be 2-(2', 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 solid-to-liquid ratio of three hydration iridous chlorides and the second solvent is 0.35～0.70g:25～50mL.The concentration of ring master metal part in the second solvent is 0.1～0.125mmol/L.
Be that 2:1～3:1 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, 1:2～1:4 will be dissolved in the 3rd solvent containing iridium chlorine bridge dipolymer and 2-pyridine carboxylic acid in molar ratio, is heated to reflux state reaction 8～20 hours, obtains blue phosphorescent iridium metal complex after separation and purification.
The 3rd shielding gas is nitrogen, argon gas, helium or neon.
The 3rd solvent is cellosolvo or trichlorotoluene zotrichloride.The solid-to-liquid ratio of 2-pyridine carboxylic acid and the 3rd solvent is 0.25～0.37g:40～60mL.Containing the concentration of iridium chlorine bridge dipolymer in the 3rd solvent, be 0.01～0.025mol/L.
1:2～1:4 will be dissolved in the 3rd solvent containing iridium chlorine bridge dipolymer and 2-pyridine carboxylic acid in molar ratio, be heated to 62～135 ℃, in reflux state reaction 8～20 hours, obtain blue phosphorescent iridium metal complex after separation and purification, and reaction formula is as follows:
The method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature naturally, after removing partial solvent under reduced pressure, add methyl alcohol, filter, solid is used normal hexane, the ultrasonic lower washing of ether successively, the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to washing, and steaming desolventizes, and obtains blue phosphorescent iridium metal complex after dry.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 4-position of R substituted pyrimidines or the hydrogen on 5-position.
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 blue 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, 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') (2-pyridine formyl) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, C
2') (2-pyridine formyl) 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 20mL containing the aqueous solution of 3.31g (24mmol) salt of wormwood subsequently in reaction system.Heating, approximately 100 ℃ of stirring reaction 8h of reflux state.Reaction finishes, question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, the methylene dichloride of take carries out silica gel column chromatography separation to crude product as elutriant, 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 resulting material of the above-mentioned reaction of above data acknowledgement 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 the cellosolvo and the water mixed solution that 3:1 mixes by volume of 25mL, 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 part 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') (2-pyridine formyl) close the synthetic of complex of iridium
In nitrogen atmosphere, by 1.22g (1mmol) part, be 2-(2', 4'-difluorophenyl) being dissolved in 40mL2-ethoxy ethanol containing iridium dichloro dipolymer and 0.25g (2mmol) 2-pyridine carboxylic acid of pyrimidine, is heated to 135 ℃ of reflux states, stirring reaction 8h.Reaction finishes, reaction solution is chilled to after room temperature naturally, after removing partial solvent under reduced pressure, add appropriate methyl alcohol, filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively, and the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to washing, steaming desolventizes, after dry, obtain pure blue phosphorescence two (2-(4', 6'-difluorophenyl) pyrimidine-N, C
2') (2-pyridine formyl) close complex of iridium 0.71g, yield is 51.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 697.1 (M
+)
Ultimate analysis: C26H14F4IrN5O2
Theoretical value: C, 44.83; H, 2.03; F, 10.91; Ir, 27.59; N, 10.05; O, 4.59;
Measured value: C, 44.75; H, 2.10; F, 10.95; Ir, 27.54; N, 10.08; O, 4.58.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-difluorophenyl) pyrimidine-N, C of blue phosphorescent
2') (2-pyridine formyl) close complex of iridium.
As shown in Figure 2, 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) is at 472nm place, at 496nm place, have an acromion, this shows to observe phosphorescent emissions in the wavelength region with higher blue purity of color simultaneously, and the two (2-(4' of this blue phosphorescent are described, 6'-difluorophenyl) pyrimidine-N, C
2') (2-pyridine formyl) to close the purity of color of complex of iridium higher, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-6the CH of M end product
2cl
2solution, at 298K temperature, be take 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=0.37, blue phosphorescent two (2-(4', 6'-difluorophenyl) pyrimidine-N, the C of visible the present embodiment
2') (2-pyridine formyl) close complex of iridium and have higher luminous quantum efficiency, can improve the luminescent properties of organic electroluminescence device.
Embodiment 2
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (2-pyridine formyl) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (2-pyridine formyl) 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 40mL containing the aqueous solution of 3.18g (30mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 90 ℃ of state of temperatures.Reaction finishes, question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, the methylene dichloride of take carries out silica gel column chromatography separation to crude product as elutriant, after dry, obtain 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 resulting material of the above-mentioned reaction of above data acknowledgement 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 part 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') (2-pyridine formyl) close the synthetic of complex of iridium
In argon atmosphere, by 1.28g (1mmol) part, be 2-(2', 4'-difluorophenyl) being dissolved in 50mL2-methyl cellosolve containing iridium dichloro dipolymer and 0.37g (3mmol) 2-pyridine carboxylic acid of-5-methylpyrimidine, is heated to 125 ℃ of reflux states, stirring reaction 10h.Reaction finishes, reaction solution is chilled to after room temperature naturally, after removing partial solvent under reduced pressure, add appropriate methyl alcohol, filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively, and the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to washing, steaming desolventizes, after dry, obtain blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C
2') (2-pyridine formyl) close complex of iridium 0.80g, yield is 55.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 725.1 (M
+)
Ultimate analysis: C28H18F4IrN5O2
Theoretical value: C, 46.41; H, 2.50; F, 10.49; Ir, 26.52; N, 9.66; O, 4.42;
Measured value: C, 46.47; H, 2.41; F, 10.51; Ir, 26.55; N, 9.61; O, 4.45.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, C of blue phosphorescent
2') (2-pyridine formyl) 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 470nm place, has an acromion at 495nm 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=0.32, blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-methylpyrimidine-N, the C of visible the present embodiment
2') (2-pyridine formyl) close complex of iridium and have higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C
2') (2-pyridine formyl) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C
2') (2-pyridine formyl) 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 20mL containing the aqueous solution of 4.24g (40mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 12h under 85 ℃ of state of temperatures.Reaction finishes, question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, the methylene dichloride of take carries out silica gel column chromatography separation to crude product as elutriant, after dry, obtain 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 resulting material of the above-mentioned reaction of above data acknowledgement 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, 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-tertiary butyl pyrimidine containing iridium dichloro dipolymer 0.58g, yield is 40.2%.
Concrete reaction formula is as follows:
(3) blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C2') (2-pyridine formyl) closes the synthetic of complex of iridium
In neon atmosphere, by 1.44g (1mmol) part, be 2-(2', 4'-difluorophenyl) being dissolved in 60mL trichloromethane containing iridium dichloro dipolymer and 0.31g (2.5mmol) 2-pyridine carboxylic acid of-5-tertiary butyl pyrimidine, is heated to 62 ℃ of reflux states, stirring reaction 20h.Reaction finishes, reaction solution is chilled to after room temperature naturally, after removing partial solvent under reduced pressure, add appropriate methyl alcohol, filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively, take methylene dichloride as elutriant to washing after solid carry out silica gel column chromatography separation, steaming desolventizes, and obtains two (2-(4', 6'-the difluorophenyl)-5-tertiary butyl pyrimidine-N of pure blue phosphorescence after being dried, C2') (2-pyridine formyl) closes complex of iridium 0.63g, and yield is 38.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 809.2 (M
+)
Ultimate analysis: C34H30F4IrN5O2
Theoretical value: C, 50.49; H, 3.74; F, 9.40; Ir, 23.76; N, 8.66; O, 3.96;
Measured value: C, 50.53; H, 3.70; F, 9.43; Ir, 23.72; N, 8.69; O, 3.93.
The resulting material of the above-mentioned reaction of above data acknowledgement is that blue phosphorescent two (2-(4', 6'-difluorophenyl)-5-tertiary butyl pyrimidine-N, C2') (2-pyridine formyl) closes complex of iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 475nm place, has an acromion at 501nm 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=0.33.
Embodiment 4
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridine formyl) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridine formyl) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine is synthetic
In helium 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 palladium and is dissolved in 30mL toluene, drips 20mL containing the aqueous solution of 1.38g (10mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 10h under 100 ℃ of state of temperatures.Reaction finishes, and question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, get organic phase, is washed to neutrality, and anhydrous magnesium sulfate drying filters, and filtrate decompression steams solvent and obtains crude product.Take methylene dichloride as elutriant carries out silica gel column chromatography separation to crude product, after being dried, obtain 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 resulting material of the above-mentioned reaction of above data acknowledgement 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 helium atmosphere, by 0.35g (1mmol) three hydration iridous chlorides and 0.94g (2mmol) 2-(2', 4'-difluorophenyl)-4 eicosyl 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)-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') (2-pyridine formyl) close the synthetic of complex of iridium.
In helium atmosphere, by 1.17g (0.5mmol) part, be 2-(2', 4'-difluorophenyl)-4-eicosyl pyrimidine containing iridium dichloro dipolymer and 0.25g (2mmol) 2-pyridine carboxylic acid, be dissolved in 50mL1, in 2-ethylene dichloride, be heated to 85 ℃ of reflux states, stirring reaction 15h.Reaction finishes, reaction solution is chilled to after room temperature naturally, after removing partial solvent under reduced pressure, add appropriate methyl alcohol, filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively, and the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to washing, steaming desolventizes, after dry, obtain blue phosphorescent two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridine formyl) close complex of iridium 0.25g, yield is 19.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1257.7 (M
+)
Ultimate analysis: C66H94F4IrN5O2
Theoretical value: C, 63.03; H, 7.53; F, 6.04; Ir, 15.28; N, 5.57; O, 2.54;
Measured value: C, 63.11; H, 7.45; F, 6.09; Ir, 15.24; N, 5.53; O, 2.58.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-difluorophenyl)-4-eicosyl pyrimidine-N, C of blue phosphorescent
2') (2-pyridine formyl) 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 480nm place, has an acromion at 505nm 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=0.10.
Embodiment 5
An 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, by vacuum evaporation, preparing successively thickness on anode 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 the blue phosphorescent of embodiment 1 preparation, 6'-difluorophenyl) pyrimidine-N, C
2') (2-pyridine formyl) 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, negative electrode as 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).
By Keithley source measuring system (Keithley2400Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency that records organic electroluminescence device is 15.7%, and maximum lumen efficiency is 31.2lm/W.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a 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. 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; 1:2～1:4 is dissolved in the 3rd solvent containing iridium chlorine bridge dipolymer and 2-pyridine carboxylic acid described in molar ratio; be heated to reflux state reaction 8～20 hours; after separation and purification, obtain blue phosphorescent iridium metal complex, the structural formula of described blue phosphorescent iridium metal complex is:
3. the preparation method of blue phosphorescent iridium metal complex according to claim 2, 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 cellosolvo or trichlorotoluene zotrichloride.
4. the preparation method of blue phosphorescent iridium metal complex according to claim 2, is characterized in that, described catalyzer is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium.
5. the preparation method of blue phosphorescent iridium metal complex according to claim 2, is characterized in that, the molar weight of described catalyzer be described 2,4 difluorobenzene boric acid molar weight 3～6%.
6. the preparation method of blue phosphorescent iridium metal complex according to claim 2, 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, separatory, get organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filters, and filtrate decompression steams solvent and obtains crude product, take methylene dichloride as elutriant carries out silica gel column chromatography separation to described crude product, after being dried, must encircle master metal part.
7. the preparation method of blue phosphorescent iridium metal complex according to claim 2, 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.
8. the preparation method of blue phosphorescent iridium metal complex according to claim 2, 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, after removing partial solvent under reduced pressure, add methyl alcohol, filter, solid is used normal hexane, the ultrasonic lower washing of ether successively, the methylene dichloride of take carries out silica gel column chromatography separation as the solid of elutriant after to described washing, steaming desolventizes, and after being dried, obtains blue phosphorescent iridium metal complex.
9. 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 blue phosphorescent iridium metal complex claimed in claim 1.
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Citations (3)
| 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 |
| US20130075706A1 (en) * | 2011-09-19 | 2013-03-28 | Nitto Denko Corporation | Substituted biaryl compounds for light-emitting devices |
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Patent Citations (3)
| 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 |
| US20130075706A1 (en) * | 2011-09-19 | 2013-03-28 | Nitto Denko Corporation | Substituted biaryl compounds for light-emitting devices |
Non-Patent Citations (1)
| Title |
|---|
| GUOPING GE ET AL.: "Polymer-based blue electrophosphorescent light-emitting diodes based on a new iridium(III) diazine complex", 《SYNTHETIC METALS》, 6 March 2009 (2009-03-06) * |
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