CN104327124A - Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device - Google Patents

Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device Download PDF

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CN104327124A
CN104327124A CN201310309593.5A CN201310309593A CN104327124A CN 104327124 A CN104327124 A CN 104327124A CN 201310309593 A CN201310309593 A CN 201310309593A CN 104327124 A CN104327124 A CN 104327124A
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trifluoromethyl
blue phosphorescent
metal complex
solvent
pyridine
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周明杰
王平
张娟娟
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Abstract

The invention relates to a blue phosphorescent iridium metal complex and a preparation method thereof and an organic electroluminescent device. The blue phosphorescent iridium metal complex has a structural formula as shown in the specification, wherein R is hydrogen, alkyl with the carbon atom number of 1-20 or alkoxy with the carbon atom number of 1-20. The blue phosphorescent iridium metal complex uses 2-(2 ', 6'-di (trifluoromethyl) pyridine-4 '-yl) pyrimidine as a ring metal ligand body structure, 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole as an auxiliary ligand, pyrimidinyl is conducive to enhancement of the LUMO (lowest unoccupied molecular orbital) level, pyridyl and two electron withdrawing trifluoromethyl groups on the ring are conducive to the reduction of the HOMO (highest occupied molecular orbital) level, the luminescence wavelength can be effectively shifted to blue, the mulecular luminescence efficiency is improved, and trifluoromethyl and 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole as the high field intensity auxiliary ligand can improve the luminescent properties. The complex used in the organic electroluminescent device can improve the light emitting performance of the organic electroluminescent device.

Description

Blue phosphorescent iridium metal complex, its preparation method and organic electroluminescence device
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.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.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, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, 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 hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, 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 the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.
In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Compare with green light material with ruddiness, the development of blue light material is more delayed comparatively speaking, the breakthrough point that the efficiency improving blue light material has just become people to study with purity of color, but at present there is bottleneck problem in blue phosphor materials in the efficiency decay of illuminant colour purity, luminous efficiency and device etc., makes the luminescent properties of organic electroluminescence device poor always.Therefore, develop the blue phosphorescent organic electroluminescent material that can improve organic electroluminescence device luminescent properties and become the megatrend 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 be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
A preparation method for blue phosphorescent iridium metal complex, comprises the steps:
In the first shielding gas atmosphere, for 1:1 ~ 1:2 by structural formula be in molar ratio pyrimidine derivatives and 2,6-bis-(trifluoromethyl) pyridine-4-boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8 ~ 15 hours, obtaining structural formula after separation and purification is ring master metal part, wherein, described R is hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20;
In the second shielding gas atmosphere, be dissolved in the second solvent in molar ratio for 2:1 ~ 3:1 by described ring master metal part and three hydrated iridium trichloride, be heated to reflux state and react 24 hours, obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere; 1:2 ~ 1:3 contains iridium chlorine bridge dipolymer and 3-trifluoromethyl-5-(2 '-pyridyl)-1 by described in molar ratio; 2; 4-triazole is dissolved in the 3rd solvent; add sodium methoxide solution or alcohol sodium solution; be heated with stirring to reflux state reaction 8 ~ 20 hours, separation and purification obtains blue phosphorescent iridium metal complex, and the structural formula of described blue phosphorescent iridium metal complex is:
Wherein in an embodiment, described first solvent is tetrahydrofuran (THF), toluene or dimethyl formamide; Described second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume; Described 3rd solvent is methylene dichloride, trichloromethane or 1,2-ethylene dichloride.
Wherein in an embodiment, described catalyzer is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium.
Wherein in an embodiment, to be described structural formula be the molar weight of described catalyzer pyrimidine derivatives molar weight 3 ~ 6%; The molar weight of the carbonate in the aqueous solution of described carbonate is described structural formula 1 ~ 4 times of molar weight of pyrimidine derivatives.
Wherein in an embodiment, obtain in the step of ring master metal part after described separation and purification, the method for separation and purification is specially: reaction terminates, after question response liquid cooling 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, is that the ethyl acetate of 1:9 ~ 1:20 is separated for elutriant carries out silica gel column chromatography to described crude product with the mixed solvent of normal hexane with volume ratio, obtains ring master metal part after drying.
Wherein in an embodiment, obtaining structural formula after described separation and purification is containing in the step of iridium chlorine bridge dipolymer, the method for separation and purification is specially: reaction terminates, and after reaction solution is chilled to room temperature, rotates and steam except partial solvent, add distilled water, filter, solid uses distilled water, methanol wash successively, obtains structural formula to be after drying containing iridium chlorine bridge dipolymer.
Wherein in an embodiment, obtain in the step of blue phosphorescent iridium metal complex after described separation and purification, the method of separation and purification is specially: reaction terminates, after reaction solution is chilled to room temperature naturally, and concentrated remove portion solvent, impouring distilled water, there is solid to separate out, filter, collect solid, described solid uses deionized water, methanol wash successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol.
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, electron injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material, and described light emitting guest material is above-mentioned blue phosphorescent iridium metal complex.
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2 '-pyridyl)-1, 2, 4-triazole is assistant ligand, pyrimidyl is conducive to improving lumo energy, two electron withdrawing group trifluoromethyls on pyridyl and ring are conducive to reducing HOMO energy level, effective blue shift emission wavelength, improve molecular luminescence efficiency, on pyridine ring 2, two trifluoromethyls of 6-position and high field intensity assistant ligand 3-trifluoromethyl-5-(2 '-pyridyl)-1, 2, the introducing of 4-triazole can also improve luminescent properties.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the blue phosphorescent iridium metal complex of an embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C prepared by embodiment 1 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the utilizing emitted light spectrogram of complex of iridium.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The blue phosphorescent iridium metal complex of one embodiment, structural formula is as follows:
Wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
Carbonatoms be 1 ~ 20 alkyl can for straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can for unbranched alkoxy or branched alkoxy.Hydrogen on the 4-position of R substituted pyrimidines or 5-position.
The cyclic metal complexes of blue phosphorescent iridium metal complex can be following structure:
Above-mentioned blue phosphorescent iridium metal complex is with 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole for assistant ligand.Pyrimidyl is conducive to improving lumo energy, and two electron withdrawing group trifluoromethyls on pyridyl and ring are conducive to reducing HOMO energy level, effective blue shift material emission wavelength, improve molecular luminescence efficiency.On pyridine ring, two trifluoromethyls of 2,6-positions and the introducing of high field intensity assistant ligand 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole can also improve luminescent properties.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.Meanwhile, the luminescent properties of different distribution type title complex can also improve because intramolecular energy is improved, and can reduce evaporation temperature, increases film-forming type and improves the stability of device.
And, the side chain of different lengths, straight chained alkyl or side chain, unbranched alkoxy are introduced on the difference replacement position of pyrimidine ring, material solubleness in organic solvent can not only be increased, its space steric effect produced on pyrimidine ring can also reduce the interaction force between material molecule, the self-quenching phenomenon of triplet exciton in solid film will be reduced, thus satisfied luminous efficiency can be obtained, simultaneously, the introducing of alkyl or alkoxyl group is beneficial to evaporation, increases film-forming properties further and the stability of the luminescent device of this blue phosphorescent iridium metal complex of raising use.
Refer to Fig. 1, the preparation method of the blue phosphorescent iridium metal complex of an embodiment, comprises the steps S110 ~ S130.
Step S110: in the first shielding gas atmosphere, for 1:1 ~ 1:2 by structural formula be in molar ratio pyrimidine derivatives and 2,6-bis-(trifluoromethyl) pyridine-4-boric acid is dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8 ~ 15 hours, the ring master metal part obtained after separation and purification, wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
Pyrimidine derivatives in R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.Carbonatoms be 1 ~ 20 alkyl can for straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can for unbranched alkoxy or branched alkoxy.Hydrogen on the 4-position of R substituted pyrimidines or 5-position.
The structural formula of ring master metal part is wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.Carbonatoms be 1 ~ 20 alkyl can for straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can for unbranched alkoxy or branched alkoxy.Hydrogen on the 4-position of R substituted pyrimidines or 5-position.Such as, ring master metal part is specifically as follows 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine, 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine, 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine, 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-hexyloxy pyrimidine etc.
First shielding gas is nitrogen, argon gas, helium or neon.
First solvent is tetrahydrofuran (THF) (THF), toluene or dimethyl formamide (DMF).The concentration of 2,6-bis-(trifluoromethyl) pyridine-4-boric acid in the first solvent is 0.1 ~ 0.4mol/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 structural formula pyrimidine derivatives molar weight 3 ~ 6%.
The aqueous solution of carbonate is the aqueous solution of sodium carbonate or salt of wormwood.The molar weight of the carbonate in the aqueous solution of carbonate is structural formula 1 ~ 4 times of molar weight of pyrimidine derivatives.
Be that pyrimidine derivatives and 2,6-bis-(trifluoromethyl) pyridine-4-boric acid are dissolved in the first solvent by 1:1 ~ 1:2 in molar ratio, add catalyzer, drip the aqueous solution of carbonate, heating, stirs 8 ~ 15 hours, carry out Suzuki linked reaction, after separation and purification, obtain ring master metal part.The reaction formula of above-mentioned Suzuki linked reaction is as follows:
Preferably, at 85 ~ 100 DEG C, stirring carries out Suzuki linked reaction 8 ~ 15 hours.
The method of separation and purification is specially: reaction terminates, after question response liquid cooling 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, is that the ethyl acetate of 1:9 ~ 1:10 is separated for elutriant carries out silica gel column chromatography to described crude product with the mixed solvent of normal hexane with volume ratio, obtains ring master metal part after drying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Step S120: in the second shielding gas atmosphere, be dissolved in the second solvent in molar ratio for 2:1 ~ 3:1 by ring master metal part and three hydrated iridium trichloride, is heated to reflux state and reacts 24 hours, obtains containing iridium chlorine bridge dipolymer after separation and purification.
Structural formula containing iridium chlorine bridge dipolymer is r in structural formula is hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.Carbonatoms be 1 ~ 20 alkyl can for straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can for unbranched alkoxy or branched alkoxy.Hydrogen on the 4-position of R substituted pyrimidines or 5-position.Such as, can be 2-(2 ' for part containing iridium chlorine bridge dipolymer, 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine be 2-(2 ' containing iridium dichloro dipolymer, part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine be 2-(2 ' containing iridium dichloro dipolymer, part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine containing iridium dichloro dipolymer, part be 2-(2 ', 6 '-two (trifluoromethyl) pyridin-4-yl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer etc.
Second shielding gas is nitrogen, argon gas, helium or neon.
Second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume.The concentration of three hydrated iridium trichloride in the second solvent is 0.01 ~ 0.125mol/L.
Be that 2:1 ~ 3:1 is by ring master metal part and three hydrated iridium trichloride (IrCl in molar ratio 33H 2o) be dissolved in the second solvent, be heated to reflux state and react 24 hours, obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer, reaction formula is as follows:
The method of separation and purification is specially: reaction terminates, and after reaction solution is chilled to room temperature, rotates and steam except partial solvent, add distilled water, filter, solid uses distilled water, methanol wash successively, obtains containing iridium chlorine bridge dipolymer after drying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Step S130: in the 3rd shielding gas atmosphere; 1:2 ~ 1:3 will containing iridium chlorine bridge dipolymer and 3-trifluoromethyl-5-(2 '-pyridyl)-1 in molar ratio; 2; 4-triazole is dissolved in the 3rd solvent; add sodium methoxide solution or alcohol sodium solution; be heated with stirring to reflux state reaction 8 ~ 20 hours, separation and purification obtains blue phosphorescent iridium metal complex.
3rd shielding gas is nitrogen, argon gas, helium or neon.
3rd solvent is methylene dichloride, trichloromethane or 1,2-ethylene dichloride.Be 0.01 ~ 0.02mol/L containing the concentration of iridium chlorine bridge dipolymer in the 3rd solvent.
The solvent of sodium methoxide solution or alcohol sodium solution is trichloromethane, methylene dichloride or 1,2-ethylene dichloride.
The molar weight of sodium methylate or sodium ethylate is 8 ~ 12 times of the molar weight containing iridium chlorine bridge dipolymer.
1:2 ~ 1:3 will containing iridium chlorine bridge dipolymer and 3-trifluoromethyl-5-(2 '-pyridyl)-1 in molar ratio, 2,4-triazole is dissolved in the 3rd solvent, drip sodium methoxide solution or alcohol sodium solution, be heated with stirring to reflux state reaction 8 ~ 20 hours, separation and purification obtains blue phosphorescent iridium metal complex.
Concrete reaction formula is as follows:
Preferably, be heated with stirring to 40 ~ 84 DEG C, reflux state reaction 8 ~ 20 hours.
The method of separation and purification is specially: reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, impouring distilled water, there is solid to separate out, filter, collect solid, described solid uses deionized water, methanol wash successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol.
The structural formula of blue phosphorescent iridium metal complex is:
Wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
Carbonatoms be 1 ~ 20 alkyl can for straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can for unbranched alkoxy or branched alkoxy.Hydrogen on the 4-position of R substituted pyrimidines or 5-position.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Preparation method's reaction conditions of above-mentioned blue phosphorescent iridium metal complex is gentle, and lower to equipment requirements, preparation cost is low, is easy to extensive preparation.
Refer to Fig. 2, the organic electroluminescence device 300 of one embodiment, comprises the substrate 301, anode 302, hole injection layer 303, hole transmission layer 304, electronic barrier layer 305, luminescent layer 306, hole blocking layer 307, electron transfer layer 308, electron 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, electron injection buffer layer 309 and negative electrode 310 is respectively the common used material of this area.Such as, 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 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), the material of hole transmission layer 304 is N, N '-bis-(1-naphthyl)-N, N '-diphenylbenzidine (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 electron injection buffer layer 309 is lithium fluoride (LiF), the material of negative electrode 309 is metallic aluminium (Al).
The material of luminescent layer 305 comprises light emitting host material and is doped in the light emitting guest material in light emitting host material.Wherein, light emitting guest material is above-mentioned blue phosphorescent iridium metal complex, and light emitting host material is two (9-carbazyl) benzene (mCP) of 1,3-.The mass percent that light emitting guest material accounts for light emitting host material is 7%.
Above-mentioned blue phosphorescent iridium metal complex and light emitting host material 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 containing high color purity in luminescent layer 306, thus high purity blue light can be launched, and this blue phosphorescent iridium metal complex is conducive to the transferring charge in balancing device, can improve the electroluminescent properties of organic electroluminescence device 300.
It is below specific embodiment.
Embodiment 1
Blue phosphorescent two (2-(2 ', 6'-bis-(trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine
In nitrogen atmosphere, by 0.80g (5mmol) 2-bromo pyrimi piperidine, 1.55g (6mmol) 2,6-bis-(trifluoromethyl) pyridine-4-boric acid and 0.35g (0.3mmol) four (triphenyl phosphorus) close palladium and are dissolved in 15mL toluene, drip the aqueous solution of 10mL containing 1.66g (12mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 8h under 100 DEG C of state of temperatures.Reaction terminates, after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, be that the ethyl acetate of 1:20 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, obtain 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine 0.70g after drying, yield is 47.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 293.0 (M +)
Ultimate analysis: C11H5F6N3
Theoretical value: C, 45.07; H, 1.72; F, 38.88; N, 14.33;
Measured value: C, 45.15; H, 1.63; F, 38.94; N, 14.28.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine
In nitrogen atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 0.73g (2.5mmol) 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine is dissolved in the mixed solution of 25mL2-ethoxy ethanol and water 3:1 mixing by volume, is heated to stirring reaction 24h under reflux state.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine containing iridium dichloro dipolymer 0.46g, yield is 56.6%.
Concrete reaction formula is as follows:
(3) blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2 ' by 0.81g (0.5mmol) part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine containing iridium dichloro dipolymer and 0.27g (1.2mmol) 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is dissolved in 15mL trichloromethane, drip the chloroform soln of 10mL containing 0.27g (5mmol) sodium methylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 15h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the solid after washing obtains the two (2-(2 ' of 0.43g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium, yield is 43.4%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 990.1 (M +)
Ultimate analysis: C30H12F15IrN10
Theoretical value: C, 36.41; H, 1.22; F, 28.79; Ir, 19.42; N, 14.15;
Measured value: C, 36.33; H, 1.29; F, 28.84; Ir, 19.38; N, 14.16.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium.
As shown in Figure 3, transverse axis is wavelength (Wavelength, unit nm), 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 487nm place simultaneously, and this blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, C are described 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the purity of color of complex of iridium higher, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10 -6the CH of M end product 2cl 2solution at 298K temperature, with concentration for ~ 10 -6the CH of the FIrpic of M 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.30, blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji) pyrimidine-N, the C of visible the present embodiment 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium and have higher luminous quantum efficiency.
Embodiment 2
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine
In argon atmosphere, by bromo-for 0.86g (5mmol) 2-5-methylpyrimidine, 1.29g (5mmol) 2,6-bis-(trifluoromethyl) pyridine-4-boric acid and 0.18g (0.25mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 30mL DMF, drip the aqueous solution of 20mL containing 1.59g (15mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 90 DEG C of state of temperatures.Reaction terminates, after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, be that the ethyl acetate of 1:15 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, obtain 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine 0.67g after drying, yield is 43.6%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 307.1 (M +)
Ultimate analysis: C12H7F6N3
Theoretical value: C, 46.92; H, 2.30; F, 37.11; N, 13.68;
Measured value: C, 46.98; H, 2.22; F, 37.14; N, 13.66.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine
In argon atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 0.92g (3mmol) 2-(2 ', 6 '-two (trifluoromethyl) pyridine-3 '-Ji)-5-methylpyrimidine is dissolved in the mixed solution of 25mL2-ethoxy ethanol and water by volume 3:1 mixing, is heated to stirring reaction 24h under reflux state.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine containing iridium dichloro dipolymer 0.40g, yield is 47.6%.
Concrete reaction formula is as follows:
(3) blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium
In argon atmosphere, be 2-(2 ' by 0.84g (0.5mmol) part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine containing iridium dichloro dipolymer and 0.21g (1mmol) 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is dissolved in 20mL methylene dichloride, drip the dichloromethane solution of 10mL containing 0.27g (4mmol) sodium ethylate subsequently, stirring heating is warming up to 40 DEG C of reflux state reaction 20h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the mixed solvent recrystallization through methylene dichloride and dehydrated alcohol after washing obtains the two (2-(2 ' of 0.41g pure blue phosphorescence, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium, yield is 40.3%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1018.1 (M +)
Ultimate analysis: C32H16F15IrN10
Theoretical value: C, 37.76; H, 1.58; F, 28.00; Ir, 18.89; N, 13.76;
Measured value: C, 37.72; H, 1.64; F, 28.03; Ir, 18.83; N, 13.78.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 455nm place, has an acromion at 486nm place, with the CH of the FIrpic of same concentrations simultaneously 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.11, blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methylpyrimidine-N, the C of visible the present embodiment 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium and have higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4'-base)-5-t-butyl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6 '-two (trifluoromethyl) pyridin-4-yl)-5-t-butyl pyrimidines
In neon atmosphere, by bromo-for 1.08g (5mmol) 2-5-t-butyl pyrimidines, 2.07g (8mmol) 2,6-bis-(trifluoromethyl) pyridine-4-boric acid and 0.17g (0.15mmol) four (triphenyl phosphorus) close palladium and are dissolved in 25mL DMF, drip the aqueous solution of 10mL containing 2.12g (20mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of states.Reaction terminates, and after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, is washed to neutrality, anhydrous magnesium sulfate drying, and filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:10 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, 2-(2 ' is obtained after drying, 6 '-two (trifluoromethyl) pyridin-4-yl)-5-t-butyl pyrimidines 0.47g, yield is 26.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 349.1 (M +)
Ultimate analysis: C15H13F6N3
Theoretical value: C, 51.58; H, 3.75; F, 32.64; N, 12.03;
Measured value: C, 51.65; H, 3.63; F, 32.72; N, 12.00.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines
In neon atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 0.87g (2.5mmol) 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines and be dissolved in the mixed solution of 20mL2-ethoxy ethanol and water 3:1 mixing by volume, stirring reaction 24h at reflux.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines containing iridium dichloro dipolymer 0.26g, yield is 28.1%.
Concrete reaction formula is as follows:
(3) blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium
In neon atmosphere, be 2-(2 ' by 0.74g (0.4mmol) main part, 6 '-two (trifluoromethyl) pyridine-4 ' yl)-5-t-butyl pyrimidines containing iridium dichloro dipolymer and 0.21g (1mmol) 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is dissolved in 20mL trichloromethane, drip the chloroform soln of 10mL containing 0.33g (4.8mmol) sodium ethylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 12h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the solid after washing obtains the two (2-(2 ' of 0.29g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium, yield is 32.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1102.2 (M +)
Ultimate analysis: C38H28F15IrN10
Theoretical value: C, 41.42; H, 2.56; F, 25.86; Ir, 17.44; N, 12.71;
Measured value: C, 41.45; H, 2.52; F, 25.91; Ir, 17.37; N, 12.75.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-t-butyl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 465nm place, has an acromion at 499nm place, with the CH of the FIrpic of same concentrations simultaneously 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.14.
Embodiment 4
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6'-bis-(trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine
In helium atmosphere, by 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 2.59g (10mmol) 2,6-bis-(trifluoromethyl) pyridine-4-boric acid and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 30mL toluene, drip the aqueous solution of 20mL containing 1.38g (10mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 10h under 100 DEG C of state of temperatures.Reaction terminates, and after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, is washed to neutrality, anhydrous magnesium sulfate drying, and filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:10 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, 2-(2 ' is obtained after drying, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine 0.43g, yield is 15.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 573.3 (M +)
Ultimate analysis: C31H45F6N3
Theoretical value: C, 64.90; H, 7.91; F, 19.87; N, 7.32;
Measured value: C, 64.95; H, 7.83; F, 19.92; N, 7.30.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine
In helium atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 1.15g (2mmol) 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine and be dissolved in the mixed solution of 20mL2-ethoxy ethanol and water 3:1 mixing by volume, stirring reaction 24h at reflux.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine containing iridium dichloro dipolymer 0.19g, yield is 13.8%.
Concrete reaction formula is as follows:
(3) blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium
In helium atmosphere, be 2-(2 ' by 0.82g (0.3mmol) part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine containing iridium dichloro dipolymer and 0.19g (0.9mmol) 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is dissolved in 20mL1, in 2-ethylene dichloride, drip 10mL subsequently containing 1 of 0.16g (3mmol) sodium methylate, 2-dichloroethane solution, stirring heating is warming up to 84 DEG C of reflux state reaction 10h.Reaction terminates, and after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect solid, solid uses deionized water, methanol wash for several times successively, solid after washing obtains the two (2-(2 ' of 0.09g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium, yield is 9.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1550.7 (M +)
Ultimate analysis: C70H92F15IrN10
Theoretical value: C, 54.22; H, 5.98; F, 18.38; Ir, 12.40; N, 9.03;
Measured value: C, 54.26; H, 5.91; F, 18.44; Ir, 12.33; N, 9.06.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-eicosyl pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 482nm place, has an acromion at 517nm place, with the CH of the FIrpic of same concentrations simultaneously 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.02.
Embodiment 5
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine
In nitrogen atmosphere, by bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine, 3.11g (12mmol) 2,6-bis-(trifluoromethyl) pyridine-3-boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 10h under 90 DEG C of state of temperatures.Reaction terminates, after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, be that the ethyl acetate of 1:14 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solution of normal hexane with volume ratio, obtain 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine 1.36g after drying, yield is 42.1%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 323.1 (M +)
Ultimate analysis: C12H7F6N3O
Theoretical value: C, 44.60; H, 2.18; F, 35.27; N, 13.00; O, 4.95;
Measured value: C, 44.67; H, 2.10; F, 35.32; N, 13.02; O, 4.89.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine
In nitrogen atmosphere, by 0.70g (2mmol) three hydrated iridium trichloride and 1.29g (4mmol) 2-(2 ', 6 '-two (trifluoromethyl) pyridine-3 '-Ji)-5-methoxy pyrimidine and be dissolved in the mixed solution of 40mL2-ethoxy ethanol and water 3:1 mixing by volume, stirring reaction 24h at reflux.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine containing iridium dichloro dipolymer 0.73g, yield is 41.8%.
(3) blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2 ' by 0.87g (0.5mmol) part, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine containing iridium dichloro dipolymer and 0.27g (1.25mmol) 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is dissolved in 15mL1, in 2-ethylene dichloride, drip 10mL subsequently containing 1 of 0.27g (5mmol) sodium methylate, 2-dichloroethane solution, stirring heating is warming up to reflux state reaction 8h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the solid after washing obtains the two (2-(2 ' of 0.35g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium, yield is 33.3%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1050.1 (M +)
Ultimate analysis: C32H16F15IrN10O2
Theoretical value: C, 36.61; H, 1.54; F, 27.15; Ir, 18.31; N, 13.34; O, 3.05;
Measured value: C, 36.67; H, 1.47; F, 27.13; Ir, 18.36; N, 13.31; O, 3.06.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium.
In addition, 10 -6the CH of M end product 2cl 2solution at 298K temperature, with concentration for ~ 10 -6the CH of the FIrpic of M 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.12, blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-5-methoxy pyrimidine-N, the C of visible the present embodiment 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close complex of iridium and have higher luminous quantum efficiency.
Embodiment 6
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-hexyloxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2 ', 6 '-two (trifluoromethyl) pyridine-4 '-Ji)-4-hexyloxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2 ', 6 '-two (trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine
In nitrogen atmosphere, by 1.30g (5mmol) 2-bromo-4-hexyloxy pyrimidine, 1.29g (5mmol) 2,6-bis-(trifluoromethyl) pyridine-4-boric acid and the two chlorine two (triphenyl phosphorus) of 0.14g (0.2mmol) are closed palladium and are dissolved in 35mLDMF, drip the aqueous solution of 15mL containing 2.07g (15mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 12h under 80 DEG C of state of temperatures.Reaction terminates, after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, be washed to neutrality, anhydrous magnesium sulfate drying, filter, filtrate decompression steams solvent and obtains crude product, be that the ethyl acetate of 1:10 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, obtain 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine 0.41g after drying, yield is 20.8%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 393.1 (M +)
Ultimate analysis: C17H17F6N3O
Theoretical value: C, 51.91; H, 4.36; F, 28.98; N, 10.68; O, 4.07;
Measured value: C, 51.87; H, 4.43; F, 29.01; N, 10.61; O, 4.08.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2', 6'-bis-(trifluoromethyl) pyridin-4-yl)-4-hexyloxy pyrimidine
In nitrogen atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 0.64g (2.2mmol) 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine is dissolved in the mixed solution of 25mL2-ethoxy ethanol and water 3:1 mixing by volume, stirring reaction 24h at reflux.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2', 6'-bis-(trifluoromethyl) pyridin-4-yl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer 0.17g, yield is 16.8%.
(3) blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.81g (0.4mmol) main part, 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer and 0.17g (0.8mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 15mL methylene dichloride, drip the dichloromethane solution of 10mL containing 0.22g (3.2mmol) sodium ethylate subsequently, stirring heating is warming up to 40 DEG C of reflux state reaction 20h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the solid after washing obtains the two (2-(2' of 0.26g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium, yield is 27.3%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1190.2 (M +)
Ultimate analysis: C42H36F15IrN10O2
Theoretical value: C, 42.39; H, 3.05; F, 23.95; Ir, 16.15; N, 11.77; O, 2.69;
Measured value: C, 42.43; H, 3.03; F, 23.87; Ir, 16.18; N, 11.74; O, 2.75.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-4-hexyloxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 468nm place, has an acromion at 500nm place, with the CH of the FIrpic of same concentrations simultaneously 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.07.
Embodiment 7
Blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of complex of iridium.
Blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines
In nitrogen atmosphere, by 0.91g (2mmol) 2-bromo-5-eicosane oxygen yl pyrimidines, 0.78g (3mmol) 2,4-bis-(trifluoromethyl) pyridine-3-boric acid and 0.07g (0.06mmol) four (triphenyl phosphorus) close palladium and are dissolved in 20mL toluene, drip the aqueous solution of 10mL containing 0.21g (2mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 15h under 90 DEG C of state of temperatures.Reaction terminates, and after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, is washed to neutrality, anhydrous magnesium sulfate drying, and filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:9 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, 2-(2' is obtained after drying, 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines 0.16g, yield is 13.6%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 589.3 (M +)
Ultimate analysis: C31H45F6N3O
Theoretical value: C, 63.14; H, 7.69; F, 19.33; N, 7.13; O, 2.71;
Measured value: C, 63.21; H, 7.60; F, 19.35; N, 7.17; O, 2.67.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines
In nitrogen atmosphere, by 0.18g (0.5mmol) three hydrated iridium trichloride and 0.88g (1.5mmol) 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines is dissolved in the mixed solution of 30mL2-ethoxy ethanol and water 3:1 mixing by volume, stirring reaction 24h at reflux.Reaction terminates, after reaction solution is chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer 0.07g, yield is 10.0%.
(3) blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.56g (0.2mmol) main part, 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer and 0.19g (0.9mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 20mL trichloromethane, drip the chloroform soln of 10mL containing 0.19g (3.6mmol) sodium ethylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 15h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, and the mixed solvent recrystallization through methylene dichloride and dehydrated alcohol after washing obtains the two (2-(2' of 0.05g pure blue phosphorescence, 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium, yield is 7.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1582.7 (M +)
Ultimate analysis: C70H92F15IrN10O2
Theoretical value: C, 53.12; H, 5.86; F, 18.01; Ir, 12.14; N, 8.85; O, 2.02;
Measured value: C, 53.18; H, 5.77; F, 18.06; Ir, 12.09; N, 8.89; O, 2.01.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(2', 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 483nm place, has an acromion at 515nm place, with the CH of the FIrpic of same concentrations simultaneously 2cl 2solution is standard (Φ pL=0.26) Φ of end product, is recorded pL=0.01.
Embodiment 8
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, electron injection buffer layer and the negative electrode that stack gradually.
Wherein, substrate is glass substrate, it is 200nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as anode, on anode, prepare that thickness is 40nm successively by vacuum evaporation 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) layer is as hole injection layer, thickness is the N of 20nm, two (1-the naphthyl)-N of N'-, N '-diphenylbenzidine (NPB) layer is as hole transmission layer, thickness is 1 of 10nm, two (9-carbazyl) benzene (mCP) layer of 3-is the luminescent layer of 30nm as electronic barrier layer and thickness, the material of luminescent layer is the light emitting guest material comprising light emitting host material and be doped in light emitting host material, light emitting guest material is the two (2-(2' of blue phosphorescent prepared by embodiment 1, 6'-bis-(trifluoromethyl) pyridine-4'-base) pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium, light emitting host material is two (9-carbazyl) benzene (mCP) of 1,3-, and the mass percent that light emitting guest material accounts for light emitting host material is 7%.Three (oxine) aluminium (Alq of vacuum evaporation thickness to be 2,9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP) layers of 10nm as hole blocking layer, thickness be 35nm successively on this luminescent layer again 3) be that lithium fluoride (LiF) layer of 1nm is as electron injection buffer layer as electron transfer layer, thickness, finally on electron injection buffer layer, vacuum plating techniques of deposition thickness is adopted to be the metal Al layer of 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).
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency recording organic electroluminescence device is 5.7%, and maximum lumen efficiency is 6.8cd/A.
Embodiment 9
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, electron injection buffer layer and the negative electrode that stack gradually.
Wherein, substrate is glass substrate, it is 200nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as anode, on anode, prepare that thickness is 40nm successively by vacuum evaporation 4, 4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) layer is as hole injection layer, thickness is the N of 20nm, two (1-the naphthyl)-N of N'-, N '-diphenylbenzidine (NPB) layer is as hole transmission layer, thickness is 1 of 10nm, two (9-carbazyl) benzene (mCP) layer of 3-is the luminescent layer of 30nm as electronic barrier layer and thickness, the material of luminescent layer is the light emitting guest material comprising light emitting host material and be doped in light emitting host material, light emitting guest material is the two (2-(2' of blue phosphorescent prepared by embodiment 5, 6'-bis-(trifluoromethyl) pyridine-4'-base)-5-methoxy pyrimidine-N, C 3') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close complex of iridium, light emitting host material is two (9-carbazyl) benzene (mCP) of 1,3-, and the mass percent that light emitting guest material accounts for light emitting host material is 7%.Three (oxine) aluminium (Alq of vacuum evaporation thickness to be 2,9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP) layers of 10nm as hole blocking layer, thickness be 35nm successively on this luminescent layer again 3) be that lithium fluoride (LiF) layer of 1nm is as electron injection buffer layer as electron transfer layer, thickness, finally on electron injection buffer layer, vacuum plating techniques of deposition thickness is adopted to be the metal Al layer of 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).
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency recording organic electroluminescence device is 2.8%, and maximum lumen efficiency is 3.4cd/A.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
2. a preparation method for blue phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In the first shielding gas atmosphere, for 1:1 ~ 1:2 by structural formula be in molar ratio pyrimidine derivatives and 2,6-bis-(trifluoromethyl) pyridine-4-boric acid be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 8 ~ 15 hours, obtaining structural formula after separation and purification is ring master metal part, wherein, described R is hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20;
In the second shielding gas atmosphere, be dissolved in the second solvent in molar ratio for 2:1 ~ 3:1 by described ring master metal part and three hydrated iridium trichloride, be heated to reflux state and react 24 hours, obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere; 1:2 ~ 1:3 contains iridium chlorine bridge dipolymer and 3-trifluoromethyl-5-(2'-pyridyl)-1 by described in molar ratio; 2; 4-triazole is dissolved in the 3rd solvent; add sodium methoxide solution or alcohol sodium solution; be heated with stirring to reflux state reaction 8 ~ 20 hours, separation and purification obtains blue phosphorescent iridium metal complex, 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 first solvent is tetrahydrofuran (THF), toluene or dimethyl formamide; Described second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume; Described 3rd solvent is methylene dichloride, trichloromethane or 1,2-ethylene dichloride.
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, to be described structural formula be the molar weight of described catalyzer pyrimidine derivatives molar weight 3 ~ 6%; The molar weight of the carbonate in the aqueous solution of described carbonate is described structural formula 1 ~ 4 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, obtain in the step of ring master metal part after described separation and purification, the method of separation and purification is specially: reaction terminates, after question response liquid cooling 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, be that the ethyl acetate of 1:9:1:20 is separated for elutriant carries out silica gel column chromatography to described crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain ring 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 terminates, and after reaction solution is chilled to room temperature, rotates and steam except partial solvent, add distilled water, filter, solid uses distilled water, methanol wash successively, obtains structural formula to be after drying containing iridium chlorine bridge dipolymer.
8. the preparation method of blue phosphorescent iridium metal complex according to claim 2, it is characterized in that, obtain in the step of blue phosphorescent iridium metal complex after described separation and purification, the method of separation and purification is specially: reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, impouring distilled water, solid is had to separate out, filter, collect solid, described solid uses deionized water, methanol wash successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol.
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, electron injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material, and described light emitting guest material is blue phosphorescent iridium metal complex according to claim 1.
CN201310309593.5A 2013-07-22 2013-07-22 Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device Pending CN104327124A (en)

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