CN104177417A - 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
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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 an alkoxyl group with carbon atom number being 1-20. According to the blue phosphorescence iridium metal complex, 2-(4',6'-di(trifluoromethyl)phenyl)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 trifluoromethyl groups at 4,6- sites of benzene ring of 2-(4',6'-di(trifluoromethyl)phenyl)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 to obtain satisfactory blue ray. In addition, luminescence property also can be improved and luminescence intensity can be enhanced. 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 that carbonatoms is 1～20 alkoxyl group.
A preparation method for blue phosphorescent iridium metal complex, comprises the steps:
In the first shielding gas atmosphere, for 1:1～1:1.5 by structural formula be in molar ratio
pyrimidine derivatives and 2,4-bis-(trifluoromethyl) phenylo boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 10～15 hours, after separation and purification, obtain structural formula and be
ring master metal part, wherein, described R is that carbonatoms is 1～20 alkoxyl group;
In the second shielding gas atmosphere, for 2.2:1～2.5:1, 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 22～25 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 1:2.2～2.5, and the described mol ratio containing iridium chlorine bridge dipolymer and four (1-pyrazoles) boronation potassium is 1:2～3, and the structural formula of described blue phosphorescent iridium metal complex is:
In an embodiment, described the first solvent is 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 or trichloromethane; 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 4～6%; The molar weight of the carbonate in the aqueous solution of described carbonate is that described structural formula is
2～2.5 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, and the crude product after washing obtains blue phosphorescent iridium metal complex with the mixed solution recrystallization of methyl alcohol and methylene dichloride.
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, 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 above-mentioned blue phosphorescent iridium metal complex.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine is cyclic metal complexes agent structure, taking four (1-pyrazoles) change boron as assistant ligand, 2-(4', 6'-bis-(trifluoromethyl) phenyl) on the phenyl ring of pyrimidine 4, two trifluoromethyls 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, improve luminous intensity.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'-bis-(trifluoromethyl) phenyl)-5-methoxy 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 that carbonatoms is 1～20 alkoxyl group.
Carbonatoms is that 1～20 alkyl can straight chain alkoxyl group or branched alkoxy.Hydrogen on 4-position or the 5-position of R substituted pyrimidines.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine is cyclic metal complexes agent structure, taking four (1-pyrazoles) change boron as assistant ligand, 2-(4', 6'-bis-(trifluoromethyl) phenyl) on the phenyl ring of pyrimidine 4, two strong electron-withdrawing substituent trifluoromethyls of 6-position and high field intensity assistant ligand four (1-pyrazoles) are changed the introducing blue shift emission wavelength effectively of boron, 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.Meanwhile, trifluoromethyl and four (1-pyrazoles) is changed the introducing of boron and can also reduce the evaporation temperature of material, is conducive to evaporation, increases film-forming properties and improves the stability of device.
And, typical electron-donating group alkoxyl group 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 alkoxyl group 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 1:1～1:1.5 by structural formula be in molar ratio
pyrimidine derivatives and 2,4-bis-(trifluoromethyl) phenylo boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 10～15 hours, after separation and purification, obtain encircling master metal part, wherein, R is that carbonatoms is 1～20 alkoxyl group.
Pyrimidine derivatives
in R be that carbonatoms is 1～20 alkoxyl group.Carbonatoms is that 1～20 alkoxyl group can straight chained alkyl or branched-chain alkyl.Hydrogen on 4-position or the 5-position of R substituted pyrimidines.
The structural formula of ring master metal part 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.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 toluene or dimethyl formamide (DMF).The concentration of 2,4-bis-(trifluoromethyl) phenylo boric acid in the first solvent is 0.2～0.25mol/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).
The molar weight of catalyzer is that structural formula is
pyrimidine derivatives molar weight 4～6%.
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 0.5～1.0mmol/mL.The molar weight of the carbonate in the aqueous solution of carbonate is that structural formula is
2～2.5 times of molar weight of pyrimidine derivatives.
Be that 1:1～1:1.5 is by pyrimidine derivatives and 2 in molar ratio, 4-bis-(trifluoromethyl) phenylo boric acid is dissolved in the first solvent, add catalyzer, drip the aqueous solution of carbonate, heating, under reflux state, stir 10～15 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, the hydrogen on 4-position or the 5-position of R substituted pyrimidines.
For example, ring master metal part is specifically as follows 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine, 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine, 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines 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, described 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, 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 22～25 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.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'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine be 2-(2' containing iridium dichloro dipolymer, part, 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer, part be 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen 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 0.0625～0.088mmol/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 22～25 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 3rd solvent is methylene dichloride or trichloromethane.Be 0.005～0.02mol/L containing the concentration of iridium chlorine bridge dipolymer in the 3rd solvent.
The 4th solvent is acetonitrile.The concentration of four (1-pyrazoles) boronation potassium in the 4th solvent is 0.01～0.06mol/L.
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 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:
Wherein, the concentration of the methanol solution of trifluoroacetic acid silver is 0.02～0.06mol/L.Mol ratio containing iridium chlorine bridge dipolymer and trifluoroacetic acid silver is 1:2.2～2.5.Mol ratio containing iridium chlorine bridge dipolymer and four (1-pyrazoles) boronation potassium is 1:2～3.
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, and the crude product after washing obtains blue phosphorescent iridium metal complex with the mixed solution recrystallization of methyl alcohol and methylene dichloride.
The structural formula of blue phosphorescent iridium metal complex is:
Wherein, R is that carbonatoms is 1～20 alkoxyl group.
Carbonatoms is that 1～20 alkoxyl group can straight chain alkoxyl group or branched alkoxy.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'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine is synthetic
In nitrogen atmosphere, by the bromo-5-methoxy pyrimidine of 0.94g (5mmol) 2-, 1.55g (6mmol) 2,4-bis-(trifluoromethyl) phenylo boric acid and 0.29g (0.25mmol) four (triphenyl phosphorus) close palladium and are dissolved in 30mL DMF, drip the aqueous solution of 15mL containing 1.27g (12mmol) sodium carbonate subsequently in reaction system.Heating, stirring reaction 10h 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'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine 0.61g, yield is 37.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 322.0 (M
+)
Ultimate analysis: C13H8F6N2O
Theoretical value: C, 48.46; H, 2.50; F, 35.38; N, 8.69; O, 4.97;
Measured value: C, 48.42; H, 2.55; F, 35.33; N, 8.72; O, 4.98.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine
In nitrogen atmosphere, by 0.36g (1mmol) three hydration iridous chlorides and 0.77g (2.4mmol) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine is dissolved in 30mL2-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'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine containing iridium dichloro dipolymer 0.41g, yield is 47.1%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy 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 0.87g (0.5mmol) part, 4'-bis-(trifluoromethyl) phenyl) being dissolved in 30mL methylene dichloride containing iridium dichloro dipolymer of pyrimidine, at room temperature drip subsequently the methanol solution of 20mL containing 0.24g (1.1mmol) 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 0.48g (1.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 25mL acetonitrile to back flow reaction 24h.Reaction finishes, reaction solution is chilled to after room temperature, filter, filter residue with appropriate 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, and the product after washing obtains the two (2-(4' of blue phosphorescent with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.19g, productive rate is 17.1%.
Net reaction is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1114.2 (M
+)
Ultimate analysis: C38H26BF12IrN12O2
Theoretical value: C, 40.98; H, 2.35; B, 0.97; F, 20.47; Ir, 17.26; N, 15.09; O, 2.87;
Measured value: C, 40.98; H, 2.35; B, 0.97; F, 20.47; Ir, 17.26; N, 15.09; O, 2.87.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy 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 456nm place, has an acromion at 488nm place simultaneously, and blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine-N, C are described
2') (four (1-pyrazoles) change boron) to close the purity of color of complex of iridium higher, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, 10
-6the 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=0.28, blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy 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, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
Embodiment 2
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine
In argon atmosphere, by the bromo-4-hexyloxy of 1.30g (5mmol) 2-pyrimidine, 1.93g (7.5mmol) 2,4-bis-(trifluoromethyl) phenylo boric acid and the two chlorine two of 0.21g (0.3mmol) (triphenyl phosphorus) close palladium and are dissolved in 30mL toluene, drip the aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 12h 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'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine 0.49g, yield is 25.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 392.1 (M
+)
Ultimate analysis: C18H18F6N2O
Theoretical value: C, 55.10; H, 4.62; F, 29.05; N, 7.14; O, 4.08;
Measured value: C, 55.10; H, 4.62; F, 29.05; N, 7.14; O, 4.08.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine.
(2) part is the synthesizing containing iridium dichloro dimer thing of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine
In argon atmosphere, by 0.35g (1mmol) three hydration iridous chlorides and 0.86g (2.2mmol) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine is dissolved in 25mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 22h 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'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer thing 0.18g, yield is 17.8%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine-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 0.40g (0.2mmol) part, 4'-bis-(trifluoromethyl) phenyl) being dissolved in 20mL methylene dichloride containing iridium dichloro dimer of-4-hexyloxy pyrimidine, at room temperature drip subsequently the methanol solution of 10mL containing 0.11g (0.48mmol) 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 argon atmosphere, residue and 0.16g (0.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile to back flow reaction 22h.Reaction finishes, reaction solution is chilled to room temperature, filter, filter residue with appropriate washed with dichloromethane repeatedly, merging filtrate, rotation is steamed and is desolventized, obtain crude product, crude product is used to methyl alcohol, deionized water wash successively, the solid after washing obtains the two (2-(4' of blue phosphorescent with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-bis-(trifluoromethyl) phenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.06g, productive rate is 12.0%.
Net reaction is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1254.3 (M
+)
Ultimate analysis: C48H46BF12IrN12O2
Theoretical value: C, 45.98; H, 3.70; B, 0.86; F, 18.18; Ir, 15.33; N, 13.40; O, 2.55;
Measured value: C, 45.93; H, 3.77; B, 0.82; F, 18.24; Ir, 15.31; N, 13.41; O, 2.52.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-hexyloxy 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 463nm place, has an acromion at 498nm 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=0.13.
Embodiment 3
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium.
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines is synthetic
In neon atmosphere, by the bromo-5-eicosane of 0.91g (2mmol) 2-oxygen yl pyrimidines, 0.52g (2mmol) 2,4-bis-(trifluoromethyl) phenylo boric acid and 0.10g (0.08mmol) four (triphenyl phosphorus) close palladium and are dissolved in 20mL toluene, drip the aqueous solution of 10mL containing 0.69g (5mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 15h 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'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines 0.38g, yield is 16.1%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 588.4 (M
+)
Ultimate analysis: C32H46F6N2O
Theoretical value: C, 65.29; H, 7.88; F, 19.36; N, 4.76; O, 2.72;
Measured value: C, 65.33; H, 7.82; F, 19.39; N, 4.71; O, 2.75.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines.
(2) part is the synthesizing containing iridium dichloro dipolymer of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines
In neon atmosphere, by 0.18g (0.5mmol) three hydration iridous chlorides and 0.74g (1.25mmol) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines is dissolved in 20mL2-ethoxy ethanol and the water mixed solution that 3:1 mixes by volume, stirring reaction 25h 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'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer 0.16g, yield is 11.4%.
Concrete reaction formula is as follows:
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines-N, C of blue phosphorescent
2') (four (1-pyrazoles) change boron) close the synthetic of complex of iridium
In neon atmosphere, be 2-(2' by 0.28g (0.1mmol) part, 4'-difluorophenyl) being dissolved in 20mL trichloromethane containing iridium dichloro dimer of-4-eicosane oxygen yl pyrimidines, at room temperature drip subsequently the methanol solution of 10mL containing 0.06g (0.25mmol) 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 neon atmosphere, residue and 0.07g (0.2mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile to back flow reaction 25h.Reaction finishes, reaction solution is chilled to room temperature, filter, filter residue with appropriate 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, and the crude product after washing obtains the two (2-(4' of blue phosphorescent with the mixed solution recrystallization of methyl alcohol and methylene dichloride, 6'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close complex of iridium 0.03g, productive rate is 9.1%.
Net reaction is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1646.8 (M
+)
Ultimate analysis: C76H102BF12IrN12O2
Theoretical value: C, 55.43; H, 6.24; B, 0.66; F, 13.84; Ir, 11.67; N, 10.21; O, 1.94;
Measured value: C, 55.45; H, 6.21; B, 0.69; F, 13.80; Ir, 11.70; N, 10.24; O, 1.91.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-eicosane oxygen yl pyrimidines-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 477nm place, has an acromion at 508nm 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=0.08.
Embodiment 4
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'-bis-(trifluoromethyl) phenyl)-5-methoxy 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 5.1%, and maximum lumen efficiency is 7.3lm/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 that carbonatoms is 1～20 alkoxyl group.
2. a preparation method for blue phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In the first shielding gas atmosphere, for 1:1～1:1.5 by structural formula be in molar ratio
pyrimidine derivatives and 2,4-bis-(trifluoromethyl) phenylo boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 10～15 hours, after separation and purification, obtain structural formula and be
ring master metal part, wherein, described R is that carbonatoms is 1～20 alkoxyl group;
In the second shielding gas atmosphere, for 2.2:1～2.5:1, 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 22～25 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 1:2.2～2.5, and the described mol ratio containing iridium chlorine bridge dipolymer and four (1-pyrazoles) boronation potassium is 1:2～3, and 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 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 or trichloromethane; Described the 4th solvent is acetonitrile.
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 is that described structural formula is
pyrimidine derivatives 4～6%; The molar weight of the carbonate in the aqueous solution of described carbonate is that described structural formula is
2～2.5 times of molar weight of pyrimidine derivatives.
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, 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.
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, 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, and the crude product after washing obtains blue phosphorescent iridium metal complex with the mixed solution recrystallization of methyl alcohol and methylene dichloride.
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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681828A (en) * | 2002-08-16 | 2005-10-12 | 南加利福尼亚大学 | Organic light emitting materials with anionic ligand |
| 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 |
-
2013
- 2013-05-22 CN CN201310192647.4A patent/CN104177417A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681828A (en) * | 2002-08-16 | 2005-10-12 | 南加利福尼亚大学 | Organic light emitting materials with anionic ligand |
| 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 |
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》 * |
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