CN104327123A - 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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CN104327123A
CN104327123A CN201310309591.6A CN201310309591A CN104327123A CN 104327123 A CN104327123 A CN 104327123A CN 201310309591 A CN201310309591 A CN 201310309591A CN 104327123 A CN104327123 A CN 104327123A
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blue phosphorescent
metal complex
fluoro
bis
phenyl
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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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • 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 is a same matched-type metal iridium complexes using 2-(2 ', 4'-difluoro-3'-cyano phenyl) pyrimidine as a ring metal ligand body structure, pyrimidinyl on the ring metal ligand is conducive to enhancement of the LUMO (lowest unoccupied molecular orbital) level, electron withdrawing groups comprising difluoro groups and cyanogroup on the benzene ring are conducive to the reduction of the HOMO (highest occupied molecular orbital) level, the material luminescence wavelength can be effectively shifted to blue, and the luminescent properties can also be improved by introduction of the electron withdrawing groups comprising the fluoro groups and the cyanogroup. 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 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and the fluoro-3-cyanophenylboronic acid of 2,4-bis-be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 6 ~ 12 hours, obtaining structural formula after separation and purification is ring master metal part, wherein, 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 ~ 4:1 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 by described containing iridium chlorine bridge dipolymer and structural formula is in molar ratio 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine derivatives adds in the 3rd solvent, add trifluoroacetic acid silver, be heated to reflux state, stirring reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex, and the structural formula of described blue phosphorescent iridium metal complex is:
Wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
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 cellosolvo, 2-methyl cellosolve, 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 2 ~ 5%; The molar weight of the carbonate in the aqueous solution of described carbonate is described structural formula 1 ~ 3 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 1:5 ~ 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.
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, after removing partial solvent under reduced pressure, add methyl alcohol, filter, solid uses normal hexane, ether supersound washing successively, be that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, and obtains blue phosphorescent iridium metal complex after drying.
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, 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 take 2-(2', 4'-bis-fluoro-3'-cyano-phenyl) pyrimidine as the same distribution type metal iridium complex of cyclic metal complexes agent structure.Pyrimidyl on cyclic metal complexes is conducive to improving lumo energy, on phenyl ring, strong electron-withdrawing group two F bases and cyano group are conducive to reducing HOMO energy level, make the effective blue shift of material emission wavelength, on phenyl ring, the introducing that is fluorine-based, cyano group of strong electron-withdrawing group group 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 three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C prepared by embodiment 1 2') 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 emitting phosphor material iridium metal complex can be following structure:
Above-mentioned blue phosphorescent iridium metal complex take 2-(2', 4'-bis-fluoro-3'-cyano-phenyl) pyrimidine as the same distribution type metal iridium complex of cyclic metal complexes agent structure.Pyrimidyl on cyclic metal complexes is conducive to improving lumo energy, on phenyl ring, strong electron-withdrawing group two F bases and cyano group are conducive to reducing HOMO energy level, make the effective blue shift of material emission wavelength, on phenyl ring, fluorine-based, the cyano group of strong electron-withdrawing group group is introduced and can also be improved luminescent properties.This blue phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.
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, and produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton, the electro mass-energy of giving of alkyl and alkoxyl group obtains satisfied blue light emitting wavelength, 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 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and 2, the fluoro-3-cyanophenylboronic acid of 4-bis-is dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 6 ~ 12 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', the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine, 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine, 2-(2', 4'-bis-fluoro-3'-cyano-phenyl)-5-methoxy pyrimidine, 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-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 the fluoro-3-cyanophenylboronic acid of 2,4-bis-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 2 ~ 5%.
The aqueous solution of carbonate is the aqueous solution of sodium carbonate or salt of wormwood.The volumetric molar concentration of the aqueous solution of carbonate is 0.5 ~ 1.5mmol/mL.The molar weight of the carbonate in the aqueous solution of carbonate is structural formula 1 ~ 3 times of molar weight of pyrimidine derivatives.
Be that pyrimidine derivatives and the fluoro-3-cyanophenylboronic acid of 2,4-bis-are dissolved in the first solvent by 1:1 ~ 1:1.5 in molar ratio, add catalyzer, drip the aqueous solution of carbonate, heating, stirs 6 ~ 12 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 6 ~ 12 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 1:5 ~ 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 ~ 4:1 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, the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine be 2-(2' containing iridium dichloro dipolymer, part, the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine be 2-(2' containing iridium dichloro dipolymer, part, 4'-bis-fluoro-3'-cyano-phenyl)-5-methoxy pyrimidine containing iridium dichloro dipolymer, part be 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-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 ring master metal part in the second solvent is 0.1 ~ 0.2mmol/L.
Be that 2:1 ~ 4:1 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 2-(2' in molar ratio; the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine derivatives is dissolved in the 3rd solvent; add trifluoroacetic acid silver; be heated to reflux state; stirring reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex.
The structural formula of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine derivatives 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.
3rd shielding gas is nitrogen, argon gas, helium or neon.
3rd solvent is cellosolvo, 2-methyl cellosolve, 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 concentration of trifluoroacetic acid silver in the 3rd solvent is 0.01 ~ 0.02mol/L.
1:2 ~ 1:3 will containing iridium chlorine bridge dipolymer and 2-(2' in molar ratio, the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine is dissolved in the 3rd solvent, adds trifluoroacetic acid silver, be heated to reflux state, stirring reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex.
Concrete reaction formula is as follows:
Preferably, be heated to 62 ~ 135 DEG C, reflux state stirring reaction 5 ~ 10 hours.
The method of separation and purification is specially: reaction terminates, after reaction solution is chilled to room temperature naturally, methyl alcohol is added after removing partial solvent under reduced pressure, filter, solid uses normal hexane, ether supersound washing successively, be that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, and obtains blue phosphorescent iridium metal complex after drying.
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, two (1-the naphthyl)-N of 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 three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine
In nitrogen atmosphere, by 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.20g (12mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system.Heating, stirring reaction 6h 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 1:6 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine 1.04g after drying, yield is 47.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 217.0 (M +)
Ultimate analysis: C11H5F2N3
Theoretical value: C, 60.83; H, 2.32; F, 17.50; N, 19.35;
Measured value: C, 60.88; H, 2.24; F, 17.56; N, 19.32.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine
In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.54g (2.5mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine is dissolved in the mixed solution of 20mL2-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', the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine containing iridium dichloro dipolymer 0.36g, yield is 54.5%.
Concrete reaction formula is as follows:
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C 2') close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.66g (0.5mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine containing iridium dichloro dipolymer, 0.21g (1mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-) pyrimidine and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 20mL2-ethoxy ethanol, be heated to 135 DEG C of reflux states, stirring reaction 5h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C is obtained after drying 2') closing complex of iridium 0.43g, yield is 51.1%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 841.1 (M +)
Ultimate analysis: C33H12F6IrN9
Theoretical value: C, 47.14; H, 1.44; F, 13.56; Ir, 22.86; N, 14.99;
Measured value: C, 47.08; H, 1.53; F, 13.52; Ir, 22.89; N, 14.98.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C 2') 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 453nm place, has an acromion at 477nm place simultaneously, this blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, C is described 2') 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=0.35, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-) pyrimidine-N, the C of visible the present embodiment 2') close complex of iridium there is higher luminous quantum efficiency.
Embodiment 2
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methylpyrimidine
In argon atmosphere, by bromo-for 1.73g (10mmol) 2-5-methylpyrimidine, 1.83g (10mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 8h 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 1:8 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methylpyrimidine 0.92g after drying, yield is 39.8%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 231.1 (M +)
Ultimate analysis: C12H7F2N3
Theoretical value: C, 62.34; H, 3.05; F, 16.43; N, 18.17;
Measured value: C, 62.37; H, 3.02; F, 16.47; N, 18.14.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methylpyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methylpyrimidine
In argon atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.46g (2mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine is dissolved in the mixed solution of 20mL2-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', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine containing iridium dichloro dipolymer 0.31 g, yield is 45.0%.
Concrete reaction formula is as follows:
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, C 2') close the synthesis of complex of iridium
In argon atmosphere, be 2-(2' by 0.69g (0.5mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine containing iridium dichloro dipolymer, 0.18g (1.5mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methylpyrimidine and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 25mL2-methyl cellosolve, be heated to 125 DEG C of reflux states, stirring reaction 6h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, C is obtained after drying 2') closing complex of iridium 0.41g, yield is 46.4%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 883.1 (M +)
Ultimate analysis: C36H18F6IrN9
Theoretical value: C, 48.98; H, 2.06; F, 12.91; Ir, 21.77; N, 14.28;
Measured value: C, 48.92; H, 2.15; F, 12.86; Ir, 21.81; N, 14.26.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, C 2') close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 451nm place, has an acromion at 475nm 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, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methylpyrimidine-N, the C of visible the present embodiment 2') close complex of iridium there is 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 three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-t-butyl pyrimidines
In neon atmosphere, by bromo-for 2.15g (10mmol) 2-5-t-butyl pyrimidines, 2.56g (14mmol) 2,4-bis-fluoro-3-cyanophenylboronic acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 1.06g (10mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.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 1:8 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-t-butyl pyrimidines 0.90g after drying, yield is 32.9%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 273.1 (M +)
Ultimate analysis: C15H13F2N3
Theoretical value: C, 65.93; H, 4.79; F, 13.90; N, 15.38;
Measured value: C, 65.96; H, 4.72; F, 13.96; N, 15.36.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-t-butyl pyrimidines.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-t-butyl pyrimidines
In neon atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.82g (3mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-t-butyl pyrimidines is 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', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-t-butyl pyrimidines containing iridium dichloro dipolymer 0.27g, yield is 35.0%.
Concrete reaction formula is as follows:
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C 2') close the synthesis of complex of iridium
In neon atmosphere, by 0.77g (0.5mmol) part be 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines containing iridium dichloro dipolymer, 0.34g (1.25mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-t-butyl pyrimidines and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 30mL trichloromethane, be heated to 62 DEG C of reflux states, stirring reaction 10h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C is obtained after drying 2') closing complex of iridium 0.20g, yield is 19.8%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1009.3 (M +)
Ultimate analysis: C45H36F6IrN9
Theoretical value: C, 53.56; H, 3.60; F, 11.30; Ir, 19.05; N, 12.49;
Measured value: C, 53.52; H, 3.66; F, 11.27; Ir, 19.11; N, 12.44.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C 2') close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 467nm place, has an acromion at 492nm 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=0.33.
Embodiment 4
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-eicosyl pyrimidine-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-eicosyl pyrimidine-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-eicosyl pyrimidine
In helium atmosphere, by 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.37g (7.5mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 12h under 85 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 1:5 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-eicosyl pyrimidine 0.50g after drying, yield is 20.1%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 497.4 (M +)
Ultimate analysis: C31H45F2N3
Theoretical value: C, 74.81; H, 9.11; F, 7.63; N, 8.44;
Measured value: C, 74.86; H, 9.04; F, 7.67; N, 8.43.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-eicosyl pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-eicosyl pyrimidine
In helium atmosphere, by 0.18g (0.5mmol) three hydrated iridium trichloride and 0.99g (2mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-4-eicosyl pyrimidine is dissolved in the mixed solution of 10mL2-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', the fluoro-3'-cyano-phenyl of 4'-bis-)-4-eicosyl pyrimidine containing iridium dichloro dipolymer 0.10g, yield is 16.4%.
Concrete reaction formula is as follows:
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-eicosyl pyrimidine-N, C 2') close the synthesis of complex of iridium
In helium atmosphere, be 2-(2' by 0.49g (0.2mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-)-4-eicosyl pyrimidine containing iridium dichloro dipolymer, 0.20g (0.4mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-4-eicosyl pyrimidine and 0.05g (0.2mmol) trifluoroacetic acid silver is dissolved in 20mL1, in 2-ethylene dichloride, be heated to 85 DEG C of reflux states, stirring reaction 8h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-eicosyl pyrimidine-N, C is obtained after drying 2') closing complex of iridium 0.07g, yield is 10.4%.Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1683.0 (M +)
Ultimate analysis: C93H132F6IrN9
Theoretical value: C, 66.40; H, 7.91; F, 6.78; Ir, 11.43; N, 7.49;
Measured value: C, 66.43; H, 7.83; F, 6.85; Ir, 11.46; N, 7.43.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-eicosyl pyrimidine-N, C 2') close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 479nm place, has an acromion at 505nm 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=0.06.
Embodiment 5
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methoxy pyrimidine
In nitrogen atmosphere, by bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine, 2.20g (12mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 6h 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 1:7 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methoxy pyrimidine 0.99g after drying, yield is 40.0%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 247.1 (M +)
Ultimate analysis: C12H7F2N3O
Theoretical value: C, 58.30; H, 2.85; F, 15.37; N, 17.00; O, 6.47;
Measured value: C, 58.34; H, 2.78; F, 15.43; N, 17.03; O, 6.42.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methoxy pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-methoxy pyrimidine
In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.49g (2mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methoxy pyrimidine is dissolved in the mixed solution of 20mL2-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', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methoxy pyrimidine containing iridium dichloro dipolymer 0.29g, yield is 40.3%.
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C 2') close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.72g (0.5mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methoxy pyrimidine containing iridium dichloro dipolymer, 0.25g (1mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-methoxy pyrimidine and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 25mL2-ethoxy ethanol, be heated to 135 DEG C of reflux states, stirring reaction 6h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C is obtained after drying 2') closing complex of iridium 0.37g, yield is 39.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 931.1 (M +)
Ultimate analysis: C36H18F6IrN9O3
Theoretical value: C, 46.45; H, 1.95; F, 12.25; Ir, 20.65; N, 13.54; O, 5.16;
Measured value: C, 46.49; H, 1.90; F, 12.32; Ir, 20.57; N, 13.58; O, 5.14.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C 2') 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=0.13, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, the C of visible the present embodiment 2') close complex of iridium there is higher luminous quantum efficiency.
Embodiment 6
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-hexyloxy pyrimidine-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-hexyloxy pyrimidine-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-hexyloxy pyrimidine
In nitrogen atmosphere, by 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 1.83g (10mmol) 2,4-bis-fluoro-3-cyanophenylboronic acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 40mLDMF, drip the aqueous solution of 20mL containing 1.06g (10mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 80 DEG C of states.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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-hexyloxy pyrimidine 0.88g after drying, yield is 27.7%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 317.1 (M +)
Ultimate analysis: C17H17F2N3O
Theoretical value: C, 64.34; H, 5.40; F, 11.97; N, 13.24; O, 5.04;
Measured value: C, 64.37; H, 5.33; F, 11.95; N, 13.33; O, 5.02.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-hexyloxy pyrimidine.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-4-hexyloxy pyrimidine
In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.95g (3mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-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', the fluoro-3'-cyano-phenyl of 4'-bis-)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer 0.24g, yield is 27.9%.
Concrete reaction formula is as follows:
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-hexyloxy pyrimidine-N, C 2') close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.86g (0.5mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer, 0.40g (1.25mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-4-hexyloxy pyrimidine and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 30mL1, in 2-ethylene dichloride, be heated to 84 DEG C of reflux states, stirring reaction 10h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-hexyloxy pyrimidine-N, C is obtained after drying 2') closing complex of iridium 0.19g, yield is 16.6%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1141.3 (M +)
Ultimate analysis: C51H48F6IrN9O3
Theoretical value: C, 53.68; H, 4.24; F, 9.99; Ir, 16.84; N, 11.05; O, 4.21;
Measured value: C, 53.63; H, 4.29; F, 9.93; Ir, 16.92; N, 11.01; O, 4.22.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-4-hexyloxy pyrimidine-N, C 2') close complex of iridium.
End product is CH at 298K temperature 2cl 2solution (~ 10 -6the maximum emission peak of the emmission spectrum M), at 470nm place, has an acromion at 495nm 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.
Embodiment 7
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-eicosane oxygen yl pyrimidines-N, C 2') close the synthesis of complex of iridium.
Blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-eicosane oxygen yl pyrimidines-N, C 2') to close the structural formula of complex of iridium as follows:
(1) synthesis of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-eicosane oxygen yl pyrimidines
In nitrogen atmosphere, by 2.28g (5mmol) 2-bromo-5-eicosyl pyrimidine, 1.37g (7.5mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.59g (15mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 8h 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 1:5 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-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-eicosane oxygen yl pyrimidines 0.50g after drying, yield is 19.5%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 513.3 (M +)
Ultimate analysis: C31H45F2N3O
Theoretical value: C, 72.48; H, 8.83; F, 7.40; N, 8.18; O, 3.11;
Measured value: C, 72.44; H, 8.87; F, 7.43; N, 8.14; O, 3.12.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-eicosane oxygen yl pyrimidines.
(2) part is the synthesis containing iridium dichloro dipolymer of 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-)-5-eicosane oxygen yl pyrimidines
In nitrogen atmosphere, by 0.18g (0.5mmol) three hydrated iridium trichloride and 1.03g (2mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-eicosane oxygen yl pyrimidines is dissolved in the mixed solution of 10mL2-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', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer 0.09g, yield is 14.4%.
(3) blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-eicosane oxygen yl pyrimidines-N, C 2') close the synthesis of complex of iridium
In nitrogen atmosphere, be 2-(2' by 0.50g (0.2mmol) part, the fluoro-3'-cyano-phenyl of 4'-bis-)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer, 0.31g (0.6mmol) 2-(2', the fluoro-3'-cyano-phenyl of 4'-bis-)-5-eicosane oxygen yl pyrimidines and 0.11g (0.5mmol) trifluoroacetic acid silver is dissolved in 20mL2-methyl cellosolve, under being heated to 100 DEG C of state of temperatures, stirring reaction 8h.Reaction terminates, after reaction solution is chilled to room temperature naturally, proper amount of methanol is added after removing partial solvent under reduced pressure, filter, solid uses a small amount of normal hexane, ether supersound washing successively, is that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-eicosane oxygen yl pyrimidines-N, C is obtained after drying 2') closing complex of iridium 0.05g, yield is 7.2%.
Concrete reaction formula is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1730.0 (M +)
Ultimate analysis: C93H132F6IrN9O3
Theoretical value: C, 64.55; H, 7.69; F, 6.59; Ir, 11.11; N, 7.29; O, 2.77;
Measured value: C, 64.52; H, 7.74; F, 6.56; Ir, 11.17; N, 7.25; O, 2.76.
The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent three (2-(the fluoro-5'-cyano-phenyl of 4', 6'-bis-)-5-eicosane oxygen yl pyrimidines-N, C 2') 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 509nm 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=0.05.
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 "-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 blue phosphorescent three (2-(4' prepared by embodiment 1, the fluoro-5'-cyano-phenyl of 6'-bis-) pyrimidine-N, C 2') closing 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 15.5%, and maximum lumen efficiency is 16.3cd/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 blue phosphorescent three (2-(4' prepared by embodiment 5, the fluoro-5'-cyano-phenyl of 6'-bis-)-5-methoxy pyrimidine-N, C 2') closing 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 8.6%, and maximum lumen efficiency is 9.2cd/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 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and the fluoro-3-cyanophenylboronic acid of 2,4-bis-be dissolved in the first solvent, add the aqueous solution and the catalyzer of carbonate, carry out Suzuki linked reaction 6 ~ 12 hours, obtaining structural formula after separation and purification is ring master metal part, wherein, 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 ~ 4:1 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 by described containing iridium chlorine bridge dipolymer and structural formula is in molar ratio 2-(the fluoro-3'-cyano-phenyl of 2', 4'-bis-) pyrimidine derivatives add in the 3rd solvent, add trifluoroacetic acid silver, be heated to reflux state, stirring reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex, and the structural formula of described blue phosphorescent iridium metal complex is:
Wherein, R be hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20.
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 cellosolvo, 2-methyl cellosolve, 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 2 ~ 5%; The molar weight of the carbonate in the aqueous solution of described carbonate is described structural formula 1 ~ 3 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 1:5 ~ 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, ring master metal part is obtained after drying.
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, methyl alcohol is added after removing partial solvent under reduced pressure, filter, solid uses normal hexane, ether supersound washing successively, be that elutriant carries out silica gel column chromatography separation to the solid after washing with methylene dichloride, steaming desolventizes, and obtains blue phosphorescent iridium metal complex after drying.
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.
CN201310309591.6A 2013-07-22 2013-07-22 Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device Pending CN104327123A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109295499A (en) * 2018-11-26 2019-02-01 四川大学 With the preparation method for the Full color library of molecules that Ir (pbi) 2 (acac) is skeleton

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109295499A (en) * 2018-11-26 2019-02-01 四川大学 With the preparation method for the Full color library of molecules that Ir (pbi) 2 (acac) is skeleton

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