CN104177437A - Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device - Google Patents
Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention relates to blue phosphorescence iridium complexes, a preparing method thereof and an organic electroluminescent device. The blue phosphorescence iridium complexes are characterized in that: the structure formula of the complexes is shown in the specification, wherein R is hydrogen or alkyl of C1-C20. The blue phosphorescence iridium complexes can improve electroluminescent properties of the organic electroluminescent device.
Description
Technical field
The present invention relates to electroluminescent material technical field, particularly relate to a kind of blue phosphorescent material iridium metal complex, its preparation method and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
In order to make 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 the luminescent properties of electroluminescent device.
A kind of preparation method of blue phosphorescent iridium metal complex further, is provided.
A kind of organic electroluminescence device that uses this blue phosphorescent iridium metal complex is also provided.
A blue phosphorescent iridium metal complex, has following structural formula:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
In an embodiment, structural formula is therein:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
A preparation method for blue phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In protective gas atmosphere; the compound F 17-hydroxy-corticosterone that is 1:1～1.5 by mol ratio and 2; 4-bis-(trifluoromethyl) phenylo boric acid is dissolved in the first solvent; the aqueous solution that adds organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8～15 hours; after separation and purification, obtain compd A, the structural formula of compound F 17-hydroxy-corticosterone is
the structural formula of compd A is
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20;
In protective gas atmosphere, the described compd A that is 2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent, are heated to reflux state reaction 22～25 hours, obtain compd B after separation and purification, and the structural formula of described compd B is:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20;
In protective gas atmosphere; by the compd B of mol ratio 1:2～1:2.4 and 5-(2 '-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in the 3rd solvent, adds organic bases solution, is heated to reflux state reaction 10～20 hours; after separation and purification, obtain blue phosphorescent iridium metal complex, the structural formula of described blue phosphorescent iridium metal complex is:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
In an embodiment, described the first solvent is toluene or DMF therein; Described the second solvent is the mixture of cellosolvo and water, and the volume ratio of described cellosolvo and water is 3:1; Described the 3rd solvent is cellosolvo, 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
In an embodiment, described organic palladium catalyzer is that tetra-triphenylphosphine palladium or two chlorine two (triphenyl phosphorus) close palladium therein, and the mol ratio of catalyzer and described compound F 17-hydroxy-corticosterone is 4:100～6:100 described in described organic palladium catalyzer.
In an embodiment, obtain in the step of compd A after separation and purification therein, the method for separation and purification is specially: after reacting completely, reaction solution is chilled to room temperature naturally, with dichloromethane extraction, organic phase is washed with water to neutrality, by organic phase anhydrous magnesium sulfate drying, filter organic phase, the solvent of removing in organic phase obtains oily crude product, take methylene dichloride as eluent, by oily crude product silica gel column chromatography separating-purifying, except desolventizing, the compd A after must purifying after being dried.
Therein in an embodiment, after separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature, remove at least part of the second solvent, add depositing in water to analyse, after filtering, collect solid, described solid is used to distilled water and methanol wash successively, after being dried, obtain the compd B of purifying.
Therein in an embodiment, after separation and purification, obtain in the step of blue phosphorescent iridium metal complex, the method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, remove at least part of the 3rd solvent, add depositing in water to analyse, after filtering, collect solids, described solids is used to deionized water and methanol wash successively, and the mixed solution that re-uses methylene dichloride and dehydrated alcohol carries out recrystallization and obtains pure blue phosphorescence iridium metal complex.
In an embodiment, described carbonate is selected from least one in salt of wormwood and sodium carbonate therein.
A kind of organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, the material of described luminescent layer comprises luminous material of main part and be doped in the luminous guest materials in described luminous material of main part, and described luminous guest materials is above-mentioned blue phosphorescent iridium metal complex.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2', 4'-bis-(trifluoromethyl) phenyl) pyrimidine is cyclic metal complexes agent structure, with 5-(2'-pyridyl)-1,2,3,4-tetrazolium is assistant ligand, the difference that the alkyl of the straight or branched formula of different lengths is introduced pyrimidine ring replaces on position, can not only increase the solubleness of material in ordinary organic solvents, its space steric effect producing on pyrimidine ring can also reduce the interaction force between material molecule, to reduce the self-quenching phenomenon of triplet exciton in solid film, thereby can obtain satisfied luminous efficiency; Simultaneously, on phenyl ring 4, two strong electron-withdrawing substituent trifluoromethyls of 6-position and high field intensity assistant ligand 5-(2'-pyridyl)-1,2,3, the introducing of 4-tetrazolium is blue shift emission wavelength effectively, and different luminescent properties of joining type title complex can also shift and is improved and improves because of intramolecular energy, thereby improves the electroluminescent properties of organic electroluminescence device; Meanwhile, above-mentioned blue phosphorescent iridium metal complex is beneficial to evaporation, increases film-forming type and improves the stability of organic electroluminescence device.
Accompanying drawing explanation
Preparation method's schema of the blue phosphorescent iridium metal complex of Fig. 1 mono-embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C of the blue phosphorescent of embodiment 1
2') (5-(2 '-pyridyl)-pyrrotriazole) close the utilizing emitted light spectrogram of complex of iridium;
Fig. 4 is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine-N, C of the blue phosphorescent of embodiment 2
2') (5-(2 '-pyridyl)-pyrrotriazole) close the utilizing emitted light spectrogram of complex of iridium;
Fig. 5 is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine-N, C of the blue phosphorescent of embodiment 3
2') (5-(2'-pyridyl)-pyrrotriazole) close the utilizing emitted light spectrogram of complex of iridium;
Fig. 6 is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine-N, C of the blue phosphorescent of embodiment 4
2') (5-(2'-pyridyl)-pyrrotriazole) close the utilizing emitted light spectrogram of complex of iridium.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
A blue phosphorescent iridium metal complex, its structural formula is as follows:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Preferably, R is that carbonatoms is 1～20 straight or branched alkyl.
Preferably, the structural formula of above-mentioned blue phosphorescent iridium metal complex is:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2', 4'-bis-(trifluoromethyl) phenyl) pyrimidine is cyclic metal complexes agent structure, with 5-(2'-pyridyl)-1,2,3,4-tetrazolium is assistant ligand, the difference that the alkyl of the straight or branched formula of different lengths is introduced pyrimidine ring replaces on position, can not only increase the solubleness of material in ordinary organic solvents, its space steric effect producing on pyrimidine ring can also reduce the interaction force between material molecule, to reduce the self-quenching phenomenon of triplet exciton in solid film, thereby can obtain satisfied luminous efficiency; Simultaneously, on phenyl ring 4, two strong electron-withdrawing substituent trifluoromethyls of 6-position and high field intensity assistant ligand 5-(2'-pyridyl)-1,2,3, the introducing of 4-tetrazolium is blue shift emission wavelength effectively, and different luminescent properties of joining type title complex can also shift and is improved and improves because of intramolecular energy, thereby improves the electroluminescent properties of organic electroluminescence device; Meanwhile, above-mentioned blue phosphorescent iridium metal complex is beneficial to evaporation, increases film-forming type and improves the stability of organic electroluminescence device.
Refer to Fig. 1, the preparation method of the blue phosphorescent iridium metal complex of an embodiment, comprises the steps:
Step S110: in protective gas atmosphere; the compound F 17-hydroxy-corticosterone that is 1:1～1.5 by mol ratio and 2; 4-bis-(trifluoromethyl) phenylo boric acid is dissolved in the first solvent; the aqueous solution that adds organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8～15 hours; after separation and purification, obtain compd A, the structural formula of compound F 17-hydroxy-corticosterone is
the structural formula of compd A is
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Protective gas is argon gas, helium or neon.
The first solvent is toluene, N.N-dimethyl formamide DMF or tetrahydrofuran (THF) (THF).The consumption of the first solvent is so that compound F 17-hydroxy-corticosterone and 2,4-bis-(trifluoromethyl) phenylo boric acid are fully dissolved as suitable.Preferably, the concentration of compound F 17-hydroxy-corticosterone in the first solvent is 0.07～0.125mol/L.
Organic palladium catalyzer is tetra-triphenylphosphine palladium (Pd (pph
3)
4) or two chlorine two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2).
Preferably, the mol ratio of organic palladium catalyzer and compound F 17-hydroxy-corticosterone is 4:100～6:100.
Carbonate in the aqueous solution of carbonate is sodium carbonate or salt of wormwood.The molar weight of carbonate is 2～4 times of compound F 17-hydroxy-corticosterone.
The method that separation and purification obtains compd A is specially: after reacting completely, reaction solution is chilled to room temperature naturally, with dichloromethane extraction, organic phase is washed with water to neutrality, by organic phase anhydrous magnesium sulfate drying, filter organic phase, the solvent of removing in organic phase obtains oily crude product, take methylene dichloride as eluent, by oily crude product silica gel column chromatography separating-purifying, except desolventizing, the compd A after must purifying after being dried.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Step S120: in protective gas atmosphere, the compd A that is 2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent, is heated to reflux state reaction 22～25 hours, obtains compd B after separation and purification, and the structural formula of compd B is:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Protective gas is argon gas, helium or neon.
The second solvent is the mixture of cellosolvo and water, and the volume ratio of cellosolvo and water is 3:1.The consumption of the second solvent is so that compd A and three hydration iridous chlorides are fully dissolved as suitable.Preferably, the concentration of three hydration iridous chlorides in the second solvent is 0.028～0.04mol/L
After separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, reaction solution is chilled to after room temperature, remove at least part of the second solvent, add depositing in water to analyse, after filtering, collect solid, described solid is used to distilled water and methanol wash successively, after being dried, obtain the compd B of purifying.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
Step S130: in protective gas atmosphere; by the compd B of mol ratio 1:2～1:2.4 and 5-(2 '-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in the 3rd solvent, adds organic bases solution, is heated to reflux state reaction 10～20 hours; after separation and purification, obtain blue phosphorescent iridium metal complex, the structural formula of described blue phosphorescent iridium metal complex is:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
Protective gas is argon gas, helium or neon.
The 3rd solvent is cellosolvo, 1,2-ethylene dichloride, methylene dichloride or trichloromethane.The consumption of the 3rd solvent is so that compd B and 5-(2 '-pyridyl)-pyrrotriazole is fully dissolved as suitable.Preferably, the concentration of compd B in the 3rd solvent is 0.01～0.014mol/L.
Solvent in organic bases solution is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.Organic bases in organic bases solution organic bases solution is sodium ethylate or sodium methylate.The molar weight of the organic bases in organic bases solution is 8～12 times of compd B.Organic bases solution
The method of separation and purification is specially: after separation and purification, obtain in the step of blue phosphorescent iridium metal complex, the method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, remove at least part of the 3rd solvent, add depositing in water to analyse, after filtering, collect solids, described solids is used to deionized water and methanol wash successively, the mixed solution that re-uses methylene dichloride and dehydrated alcohol carries out recrystallization and obtains pure blue phosphorescence iridium metal complex.
The method that is appreciated that separation and purification is not limited to aforesaid method, can carry out the method for separation and purification to above-mentioned reaction product all passable.
The synthetic route of above-mentioned blue phosphorescent iridium metal complex is as follows:
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 310 is metallic aluminium (Al).
The material of luminescent layer 306 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 ratio of above-mentioned blue phosphorescent iridium metal complex and luminous material of main part is 7:100.
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 should be noted that, the material of above-mentioned organic electroluminescence device Anodic 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 also can be other common used materials in the industry.
It is below specific embodiment.
Embodiment 1
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C
2') (5-(2 '-pyridyl)-pyrrotriazole) close the synthetic of complex of iridium
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C
2') (5-(2 '-pyridyl)-pyrrotriazole) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl) pyrimidine is synthetic
Under nitrogen protection; 0.79g (5mmol) 2-bromo pyrimi piperidine, 1.55g (6mmol) 2; 4-bis-(trifluoromethyl) phenylo boric acid and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 30mL tetrahydrofuran (THF), drip 10mL containing the aqueous solution of 1.38g (10mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 15h under reflux state.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, 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, after being dried, obtain solid 0.64g, yield is 43.8%.
Structural Identification:
Mass spectrum (MS m/z): 292.0 (M
+)
Ultimate analysis: C12H6F6N2
Theoretical value: C, 49.33; H, 2.07; F, 39.01; N, 9.59;
Measured value: C, 49.36; H, 2.02; F, 39.06; N, 9.56.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(2', 4'-bis-(trifluoromethyl) phenyl) pyrimidine.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 4'-bis-(trifluoromethyl) phenyl) pyrimidine
Under nitrogen protection; 0.36g (1mmol) three hydration iridous chlorides; 0.88g (3mmol) 2-(2'; 4'-bis-(trifluoromethyl) phenyl) pyrimidine and being dissolved in 30mL2-ethoxy ethanol and water mixed liquid (volume ratio of cellosolvo and water is 3:1), stirring reaction 24h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.48g, and yield is 59.2%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C of title complex
2') (5-(2 '-pyridyl)-pyrrotriazole) close the synthetic of iridium
Under nitrogen protection; 0.81g (0.5mmol) part is 2-(2'; 4'-bis-(trifluoromethyl) phenyl) pyrimidine containing iridium dichloro dimer and 0.18g (1.2mmol) 5-(2'-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in 25mL trichloromethane, drips subsequently 10mL containing the chloroform soln of 0.27g (5mmol) sodium methylate, and stirring heating is warming up to reflux state reaction 18h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.28g pure products, and yield is 30.4%.
Structural Identification:
Mass spectrum (MS m/z): 921.1 (M
+)
Ultimate analysis: C30H14F12IrN9
Theoretical value: C, 39.14; H, 1.53; F, 24.76; Ir, 20.88; N, 13.69;
Measured value: C, 39.18; H, 1.50; F, 24.72; Ir, 20.93; N, 13.67.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C of title complex
2') (5-(2 '-pyridyl)-pyrrotriazole) close iridium.
Refer to Fig. 3, Fig. 3 is two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, C of title complex
2') (5-(2 '-pyridyl)-pyrrotriazole) close the utilizing emitted light spectrogram 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
-6m, M is mol/L, lower with) in the maximum emission peak of emmission spectrum at 455nm place, at 490nm place, have an acromion simultaneously, 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=0.23, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine-N, C
2') (5-(2 '-pyridyl)-pyrrotriazole) close the synthetic of complex of iridium
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine-N, C
2') (5-(2 '-pyridyl)-pyrrotriazole) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine is synthetic
Under nitrogen protection; the bromo-5-methylpyrimidine of 0.86g (5mmol) 2-, 1.29g (5mmol) 2; 4-bis-(trifluoromethyl) phenylo boric acid and 0.35g (0.30mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip 15mL containing the aqueous solution of 2.76g (20mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 10h under reflux state.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, 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, after being dried, obtain solid 0.61g, yield is 39.8%.
Structural Identification:
Mass spectrum (MS m/z): 306.1 (M
+)
Ultimate analysis: C13H8F6N2
Theoretical value: C, 50.99; H, 2.63; F, 37.23; N, 9.15;
Measured value: C, 50.93; H, 2.67; F, 37.27; N, 9.13.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine
Under nitrogen protection; 0.35g (1mmol) three hydration iridous chlorides; 0.61g (2mmol) 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine and being dissolved in 35mL2-ethoxy ethanol and water mixed liquid (volume ratio of cellosolvo and water is 3:1), stirring reaction 22h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.46g, and yield is 54.9%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine-N, C of title complex
2') (5-(2 '-pyridyl)-pyrrotriazole) close the synthetic of iridium
Under nitrogen protection; 0.84g (0.5mmol) part is 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine containing iridium dichloro dimer and 0.16g (1.1mmol) 5-(2'-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in 30mL trichloromethane, drips subsequently 15mL containing the dichloromethane solution of 0.41g (6mmol) sodium ethylate, and stirring heating is warming up to reflux state reaction 20h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.26g pure products, and yield is 27.5%.
Structural Identification:
Mass spectrum (MS m/z): 949.1 (M
+)
Ultimate analysis: C32H18F12IrN9
Theoretical value: C, 40.51; H, 1.91; F, 24.03; Ir, 20.26; N, 13.29;
Measured value: C, 40.55; H, 1.88; F, 24.01; Ir, 20.28; N, 13.28.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methylpyrimidine-N, C of title complex
2') (5-(2 '-pyridyl)-pyrrotriazole) close iridium.
Refer to Fig. 4, end product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 453nm place, has an acromion at 489nm 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=0.20, the iridium electroluminescent organic material that contains of visible the present embodiment has 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'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine-N, C
2') (5-(2'-pyridyl)-pyrrotriazole) close the synthetic of complex of iridium
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine-N, C
2') (5-(2'-pyridyl)-pyrrotriazole) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine is synthetic
Under nitrogen protection; the bromo-5-tertiary butyl of 1.07g (5mmol) 2-pyrimidine, 1.81g (7mmol) 2; 4-bis-(trifluoromethyl) phenylo boric acid and the two chlorine two of 0.18g (0.25mmol) (triphenyl phosphorus) close palladium and are dissolved in 30mL DMF, drip 10mL containing the aqueous solution of 1.32g (12.5mmol) sodium carbonate subsequently in reaction system.Heating, stirring reaction 8h under reflux state.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, 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, after being dried, obtain solid 0.50g, yield is 28.7%.
Structural Identification:
Mass spectrum (MS m/z): 348.1 (M
+)
Ultimate analysis: C16H14F6N2
Theoretical value: C, 55.18; H, 4.05; F, 32.73; N, 8.04;
Measured value: C, 55.15; H, 4.09; F, 32.70; N, 8.06.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine
Under nitrogen protection; 0.35g (1mmol) three hydration iridous chlorides; 0.77g (2.2mmol) 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine and being dissolved in 30mL2-ethoxy ethanol and water mixed liquid (volume ratio of cellosolvo and water is 3:1), stirring reaction 25h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.38g, and yield is 41.2%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine-N, C of title complex
2') (5-(2'-pyridyl)-pyrrotriazole) close the synthetic of iridium
Under nitrogen protection; 0.92g (0.5mmol) part is 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine containing iridium dichloro dimer and 0.15g (1mmol) 5-(2'-pyridyl)-1; 2,3,4-tetrazolium is dissolved in 30mL1; in 2-ethylene dichloride; drip subsequently 10mL containing 1 of 0.27g (4mmol) sodium ethylate, 2-dichloroethane solution, stirring heating is warming up to reflux state reaction 15h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.21g pure products, and yield is 19.3%.
Structural Identification:
Mass spectrum (MS m/z): 1089.3 (M
+)
Ultimate analysis: C42H38F12IrN9
Theoretical value: C, 46.32; H, 3.52; F, 20.93; Ir, 17.65; N, 11.58;
Measured value: C, 46.32; H, 3.52; F, 20.93; Ir, 17.65; N, 11.58.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-tertiary butyl pyrimidine-N, C of title complex
2') (5-(2'-pyridyl)-pyrrotriazole) close iridium.
Refer to Fig. 5, 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 497nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.15, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 4
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine-N, C
2') (5-(2'-pyridyl)-pyrrotriazole) close the synthetic of complex of iridium
Blue phosphorescent two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine-N, C
2') (5-(2'-pyridyl)-pyrrotriazole) to close the structural formula of complex of iridium as follows:
(1) 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine is synthetic
Under nitrogen protection; the bromo-4-eicosyl of 2.20g (5mmol) 2-pyrimidine, 1.93g (7.5mmol) 2; 4-bis-(trifluoromethyl) phenylo boric acid and 0.18g (0.25mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL toluene, drip 20mL containing the aqueous solution of 1.27g (12mmol) sodium carbonate subsequently in reaction system.Heating, stirring reaction 9h under reflux state.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, 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, after being dried, obtain solid 0.51g, yield is 17.8%.
Structural Identification:
Mass spectrum (MS m/z): 572.4 (M
+)
Ultimate analysis: C32H46F6N2
Theoretical value: C, 67.11; H, 8.10; F, 19.90; N, 4.89;
Measured value: C, 67.15; H, 8.06; F, 19.93; N, 4.86.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 4'-bis-(trifluoromethyl) phenyl)-4-eicosyl yl pyrimidines
Under nitrogen protection; 0.35g (1mmol) three hydration iridous chlorides; 1.13g (2.4mmol) 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-4 eicosyl pyrimidines and being dissolved in 25mL2-ethoxy ethanol and water mixed liquid (volume ratio of cellosolvo and water is 3:1), stirring reaction 24h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively,
After dry, obtain solids 0.21g, yield is 15.3%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-eicosyl yl pyrimidines-N, C of title complex
2') (5-(2'-pyridyl)-pyrrotriazole) close the synthetic of iridium
Under nitrogen protection; 0.55g (0.2mmol) part is 2-(2'; 4'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine containing iridium dichloro dimer and 0.07g (0.48mmol) 5-(2'-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in 15mL2-ethoxy ethanol, drips subsequently 5mL containing the cellosolvo solution of 0.11g (2mmol) sodium methylate, and stirring heating is warming up to reflux state reaction 10h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.04g pure products, and yield is 6.7%.
Structural Identification:
Mass spectrum (MS m/z): 1481.7 (M
+)
Ultimate analysis: C70H94F12IrN9
Theoretical value: C, 56.74; H, 6.39; F, 15.39; Ir, 12.97; N, 8.51;
Measured value: C, 56.77; H, 6.32; F, 15.44; Ir, 12.93; N, 8.54.
The resulting material of the above-mentioned reaction of above data acknowledgement is two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-4-eicosyl pyrimidine-N, C of title complex
2') (5-(2'-pyridyl)-pyrrotriazole) close iridium.
Refer to Fig. 6, end product is CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 473nm place, has an acromion at 503nm 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=0.07, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
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 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as anode, by vacuum evaporation, preparing successively thickness on anode is 4 of 40nm, 4 ', 4 ' '-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 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, two (9-carbazyl) benzene (mCP) of 3-is electronic barrier layer 305, with the thickness luminescent layer that is 30nm, the material of luminescent layer 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 two (2-(4', 6'-bis-(trifluoromethyl) phenyl) pyrimidine-N, the C of embodiment 1 preparation
2') (5-(2 '-pyridyl)-pyrrotriazole) close complex of iridium, luminous material of main part is two (9-carbazyl) benzene (mCP) of 1,3-, two (2-(4', 6'-bis-(trifluoromethyl) phenyl)-5-methoxy pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) mass ratio of closing complex of iridium and luminous material of main part is 7:100.On this luminescent layer, vacuum evaporation thickness is 10nm 2 successively again, 9-dimethyl-4, three (oxine) aluminium (Alq that 7-phenylbenzene-phenanthrolene (BCP) is 35nm as hole blocking layer, thickness
3) as electron transfer layer, thickness, be that 1nm lithium fluoride (LiF) 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 (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%Ir title complex (30nm)/BCP (10nm)/Alq3 (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 10.1%, and maximum lumen efficiency is 9.2lm/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 (10)
1. a blue phosphorescent iridium metal complex, is characterized in that, has following structural formula:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
2. blue phosphorescent iridium metal complex according to claim 1, is characterized in that, structural formula is:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
3. a preparation method for blue phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In protective gas atmosphere; the compound F 17-hydroxy-corticosterone that is 1:1～1.5 by mol ratio and 2; 4-bis-(trifluoromethyl) phenylo boric acid is dissolved in the first solvent; the aqueous solution that adds organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8～15 hours; after separation and purification, obtain compd A, the structural formula of compound F 17-hydroxy-corticosterone is
the structural formula of compd A is
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20;
In protective gas atmosphere, the described compd A that is 2～3:1 by mol ratio and three hydration iridous chlorides are dissolved in the second solvent, are heated to reflux state reaction 22～25 hours, obtain compd B after separation and purification, and the structural formula of described compd B is:
wherein, R is the alkyl that hydrogen or carbonatoms are 1～20;
In protective gas atmosphere; by the compd B of mol ratio 1:2～1:2.4 and 5-(2 '-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in the 3rd solvent, adds organic bases solution, is heated to reflux state reaction 10～20 hours; after separation and purification, obtain blue phosphorescent iridium metal complex, the structural formula of described blue phosphorescent iridium metal complex is:
Wherein, R is the alkyl that hydrogen or carbonatoms are 1～20.
4. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, described the first solvent is toluene or DMF DMF; Described the second solvent is the mixture of cellosolvo and water, and the volume ratio of described cellosolvo and water is 3:1; Described the 3rd solvent is cellosolvo, 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
5. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, described organic palladium catalyzer is that tetra-triphenylphosphine palladium or two chlorine two (triphenyl phosphorus) close palladium, and the mol ratio of catalyzer and described compound F 17-hydroxy-corticosterone is 4:100～6:100 described in described organic palladium catalyzer.
6. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, after separation and purification, obtain in the step of compd A, the method of separation and purification is specially: after reacting completely, reaction solution is chilled to room temperature naturally, with dichloromethane extraction, organic phase is washed with water to neutrality, by organic phase anhydrous magnesium sulfate drying, filter organic phase, the solvent of removing in organic phase obtains oily crude product, take methylene dichloride as eluent, by oily crude product silica gel column chromatography separating-purifying, except desolventizing, the compd A after must purifying after being dried.
7. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, after separation and purification, obtain in the step of compd B, the method of separation and purification is specially: reaction finishes, and reaction solution is chilled to after room temperature, removes at least part of the second solvent, add depositing in water to analyse, after filtering, collect solid, described solid is used to distilled water and methanol wash successively, after being dried, obtain the compd B of purifying.
8. the preparation method of blue phosphorescent iridium metal complex according to claim 3, it is characterized in that, after separation and purification, obtain in the step of blue phosphorescent iridium metal complex, the method of separation and purification is specially: after reacting completely, question response liquid is chilled to room temperature naturally, remove at least part of the 3rd solvent, add depositing in water to analyse, after filtering, collect solids, described solids is used to deionized water and methanol wash successively, and the mixed solution that re-uses methylene dichloride and dehydrated alcohol carries out recrystallization and obtains pure blue phosphorescence iridium metal complex.
9. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, described carbonate is selected from least one in salt of wormwood and sodium carbonate.
10. an organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises luminous material of main part and be doped in the luminous guest materials in described luminous material of main part, and described luminous guest materials is the blue phosphorescent iridium metal complex described in claim 1 or 2.
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