CN104293341A - Blue phosphorescent iridium metal complex, preparation method thereof and organic electroluminescent device - Google Patents

Abstract

The invention relates to a blue phosphorescent iridium metal complex, a preparation method thereof and an organic electroluminescent device. The blue phosphorescent iridium metal complex has a following structure formula, wherein R is a hydrogen atom, an alkyl group with a carbon atom number being 1-20 or an alkoxy group with a carbon atom number being 1-20. In the blue phosphorescent iridium metal complex, 2-(3',4',5'-trifluorophenyl)pyrimidine is a cyclometal ligand major structure and 2,4-bis(trifluoromethyl)-5-(pyridine-2'-yl)pyrrole as an auxiliary ligand. A pyrimidine ring on the cyclometal major ligand and a low-vibration-frequency C-F bond on a benzene ring are beneficial for reduction of non-radiative transition probability so that a luminous efficiency of the blue phosphorescent iridium metal complex is improved. By means of introduction of the alkyl group or the alkoxy group to the pyrimidine ring, a wavelength of a blue light can be adjusted and a certain stereo-hinerance effect is generated so that triplet-state exciton self-quenching is reduced. A strong electrondrawing group, a fluorine group, and the high-field-intensity auxiliary ligand, 2,4-bis(trifluoromethyl)-5-(pyridine-2'-yl)pyrrole, can improve luminescence property.

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 shielding gas atmosphere, for 1:1 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and 3,4,5-trifluoro-benzene boric acid 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, described R is hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20;

In 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 shielding gas atmosphere; 1:2 ~ 1:3 contains iridium chlorine bridge dipolymer and 2 by described in molar ratio; 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is dissolved in the 3rd solvent; add carbonate or sodium methylate; be heated with stirring to reflux state 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 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 1:4 ~ 1:7 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, add distilled water precipitating, filter, collect solid, described solid uses deionized water, washed with diethylether successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and anhydrous methanol.

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 is with 2-(3', 4', 5'-trifluorophenyl) pyrimidine is cyclic metal complexes agent structure, with 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is assistant ligand, on the pyrimidine ring of the planar rigidity on ring master metal part and phenyl ring, the C-F key of low vibrational frequency is conducive to reducing nonradiative transition probability, improves the luminous efficiency of material; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group regulates blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths or oxyalkyl chain produce certain space steric effect in addition, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; On phenyl ring, strong electron-withdrawing group rolls into a ball fluorine-based and high field intensity assistant ligand 2, the introducing of 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles can 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-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C prepared by embodiment 1 ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the utilizing emitted light spectrogram of complex of iridium;

Fig. 4 is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C prepared by embodiment 5 ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 straight chained alkyl or branched-chain alkyl.Carbonatoms be 1 ~ 20 alkoxyl group can 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-(3', 4', 5'-trifluorophenyl) pyrimidine is cyclic metal complexes agent structure, with 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is assistant ligand, on the pyrimidine ring of the planar rigidity on ring master metal part and phenyl ring, the C-F key of low vibrational frequency is conducive to reducing nonradiative transition probability, improves the luminous efficiency of material; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group regulates blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths or oxyalkyl chain can produce certain space steric effect in addition, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; On phenyl ring, strong electron-withdrawing group group is fluorine-based can improve luminescent properties with introducing that is high field intensity assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles.Therefore, above-mentioned blue phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.

Further, by the straight chain of different lengths, branched-chain alkyl, or the difference that straight chain, branched alkoxy introduce pyrimidine ring replaces on position, can increase the solubleness of material in ordinary organic solvents, be conducive to the application of this blue phosphorescent iridium metal complex.The introducing of high field intensity assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is also beneficial to evaporation, increases film forming properties and improves the stability of device.

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 shielding gas atmosphere, for 1:1 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and 3,4,5-trifluoro-benzene boric acid 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 is 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 r 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, ring master metal part is specifically as follows 2-(3', 4', 5'-trifluorophenyl) pyrimidine, 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine, 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine, 2-(3', 4', 5'-5 trifluorophenyl)-4-hexyloxy pyrimidine etc.

Shielding gas is nitrogen, argon gas, helium or neon.

First solvent is tetrahydrofuran (THF) (THF), toluene or dimethyl formamide (DMF).The concentration of 3,4,5-trifluoro-benzene boric acid in the first solvent is 0.1 ~ 0.2mol/L.

Catalyzer is palladium catalyst, is preferably four (triphenyl phosphorus) and closes palladium (Pd (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 3,4,5-trifluoro-benzene boric acid are dissolved in the first solvent by 1:1 ~ 1:1.5 in molar ratio, add catalyzer, drip the aqueous solution of carbonate, heating, stir 6 ~ 12 hours at reflux, 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, be heated to 85 ~ 100 DEG C, stir 6 ~ 12 hours at reflux, carry out Suzuki linked reaction.

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 1:4 ~ 1:7 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 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-(3' for part containing iridium chlorine bridge dipolymer, 4', 5'-trifluorophenyl) pyrimidine containing iridium dichloro dipolymer, part be 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine be 2-(3' containing iridium dichloro dipolymer, part, 4', 5'-trifluorophenyl)-5-methoxy pyrimidine containing iridium dichloro dipolymer, part be 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer etc.

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 shielding gas atmosphere; 1:2 ~ 1:3 will containing iridium chlorine bridge dipolymer and 2 in molar ratio; 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is dissolved in the 3rd solvent; add carbonate or sodium methylate; be heated with stirring to reflux state reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex.

Shielding gas is nitrogen, argon gas, helium or neon.

3rd solvent is cellosolvo, 2-methyl cellosolve, trichloromethane or 1,2-ethylene dichloride.Be 0.1 ~ 0.2mol/L containing the concentration of iridium chlorine bridge dipolymer in the 3rd solvent.

Carbonate is sodium carbonate or salt of wormwood.Carbonate or sodium methylate and the mol ratio containing iridium chlorine bridge dipolymer are 8 ~ 12:1.

1:2 ~ 1:3 will containing iridium chlorine bridge dipolymer and 2 in molar ratio, 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is dissolved in the 3rd solvent, add carbonate or sodium methylate, be heated with stirring to reflux state reaction 5 ~ 10 hours, separation and purification obtains blue phosphorescent iridium metal complex.

Reaction formula is as follows:

Preferably, be heated to 84 ~ 135 DEG C, react 5 ~ 10 hours at reflux.

The method of separation and purification is specially: reaction terminates, after reaction solution is chilled to room temperature naturally, add distilled water precipitating, filter, collect solid, described solid uses deionized water, washed with diethylether successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and anhydrous methanol.

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''-tri-(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 306 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-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl) pyrimidine

In nitrogen atmosphere, by 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.11g (12mmol) 3,4,5-trifluoro-benzene boric acid 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, and 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 1:4 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain 2-(3', 4', 5'-trifluorophenyl) pyrimidine 1.15g, yield is 54.7%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 210.0 (M ⁺)

Ultimate analysis: C10H5F3N2

Theoretical value: C, 57.15; H, 2.40; F, 27.12; N, 13.33;

Measured value: C, 57.11; H, 2.38; F, 27.22; N, 13.29.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl) pyrimidine.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl) pyrimidine

In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.53g (2.5mmol) 2-(3', 4', 5'-trifluorophenyl) 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, and after reaction solution is chilled to room temperature, rotates and steams except partial solvent, add appropriate distilled water, filter, solid uses distilled water, methanol wash successively, and obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl) pyrimidine containing iridium dichloro dipolymer 0.36g, yield is 55.7%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In nitrogen atmosphere, be 2-(3' by 0.65g (0.5mmol) part, 4', 5'-trifluorophenyl) pyrimidine containing iridium dichloro dipolymer, 0.34g (1.2mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol, and stirring heating is warming up to 135 DEG C of reflux state reaction 6h.Reaction terminates, after reaction solution is chilled to room temperature naturally, add appropriate distilled water precipitating, filter, collect solid, solid uses deionized water, washed with diethylether successively, solid after washing obtains the two (2-(3' of 0.31g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and anhydrous methanol, 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 34.8%.

Reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 890.1 (M ⁺)

Ultimate analysis: C31H13F12IrN6

Theoretical value: C, 41.85; H, 1.47; F, 25.63; Ir, 21.61; N, 9.45;

Measured value: C, 41.81; H, 1.55; F, 25.57; Ir, 21.64; N, 9.43.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 471nm place, has an acromion at 501nm place simultaneously, and this blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C are described ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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-(3', 4', 5'-trifluorophenyl) pyrimidine-N, the C of visible the present embodiment ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium and have higher luminous quantum efficiency.

Embodiment 2

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine

In argon atmosphere, by bromo-for 1.73g (10mmol) 2-5-methylpyrimidine, 1.76g (10mmol) 3,4,5-trifluoro-benzene boric acid 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, and after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, is 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-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine 1.05g after drying, yield is 46.8%.Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 224.1 (M ⁺)

Ultimate analysis: C12H8FN3

Theoretical value: C, 58.93; H, 3.15; F, 25.42; N, 12.50;

Measured value: C, 58.97; H, 3.10; F, 25.46; N, 12.47.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine

In argon atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.45g (2mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine containing iridium dichloro dipolymer 0.36g, yield is 53.4%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In argon atmosphere, be 2-(3' by 0.67g (0.5mmol) part, 4', 5'-trifluorophenyl)-5-methylpyrimidine containing iridium dichloro dipolymer, 0.28g (1mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.55g (4mmol) salt of wormwood are dissolved in 30mL2-methyl cellosolve, and stirring heating is warming up to 100 DEG C of state of temperature reaction 8h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, filter, collect solid, solid uses deionized water, washed with diethylether for several times successively, solid after washing obtains the two (2-(3' of 0.25g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 27.2%.

Reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 918.1 (M ⁺)

Ultimate analysis: C33H17F12IrN6

Theoretical value: C, 43.19; H, 1.87; F, 24.84; Ir, 20.94; N, 9.16;

Measured value: C, 43.13; H, 1.93; F, 24.80; Ir, 20.99; N, 9.15.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 469nm 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=0.16, blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, the C of visible the present embodiment ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines

In neon atmosphere, by bromo-for 2.15g (10mmol) 2-5-t-butyl pyrimidines, 2.46g (14mmol) 3,4,5-trifluoro-benzene boric 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, and 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 1:6 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines 1.09g, yield is 40.9%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 266.1 (M ⁺)

Ultimate analysis: C14H13F3N2

Theoretical value: C, 63.15; H, 4.92; F, 21.41; N, 10.52;

Measured value: C, 63.10; H, 4.98; F, 21.36; N, 10.56.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines

In neon atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.80g (3mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines containing iridium dichloro dipolymer 0.30g, yield is 39.6%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In neon atmosphere, be 2-(3' by 0.61g (0.4mmol) part, 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines containing iridium dichloro dimer, 0.28g (1mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.51g (4.8mmol) sodium carbonate are dissolved in 30mL2-ethoxy ethanol, and stirring heating reacts 9h under being warming up to 90 DEG C of state of temperatures.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, filter, collect solid, solid uses deionized water, washed with diethylether for several times successively, solid after washing obtains the two (2-(3' of 0.13g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 16.2%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1002.2 (M ⁺)

Ultimate analysis: C39H29F12IrN6

Theoretical value: C, 46.75; H, 2.92; F, 22.76; Ir, 19.19; N, 8.39;

Measured value: C, 46.72; H, 2.96; F, 22.71; Ir, 19.26; N, 8.35.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 476nm place, has an acromion at 507nm 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=0.22.

Embodiment 4

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine

In helium atmosphere, by 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.19g (7.5mmol) 3,4,5-trifluoro-benzene boric acid 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, and 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 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine 0.66g, yield is 26.9%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 490.3 (M ⁺)

Ultimate analysis: C30H45F3N2

Theoretical value: C, 73.43; H, 9.24; F, 11.62; N, 5.71;

Measured value: C, 73.40; H, 9.29; F, 11.55; N, 5.76.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine

In helium atmosphere, by 0.18g (0.5mmol) three hydrated iridium trichloride, 0.98g (2mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine containing iridium dichloro dipolymer 0.13g, yield is 21.5%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In helium atmosphere, be 2-(3' by 0.72g (0.3mmol) part, 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine containing iridium dichloro dipolymer and 0.13g (0.9mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles 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, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, solid after washing obtains the two (2-(3' of 0.05g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 5.7%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1450.7 (M ⁺)

Ultimate analysis: C71H93F12IrN6

Theoretical value: C, 58.78; H, 6.46; F, 15.71; Ir, 13.25; N, 5.79;

Measured value: C, 58.75; H, 6.51; F, 15.65; Ir, 13.33; N, 5.76.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 485nm place, has an acromion at 516nm 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=0.04.

Embodiment 5

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine

In nitrogen atmosphere, by bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine, 2.11g (12mmol) 3,4,5-trifluoro-benzene boric acid 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, and after question response liquid cooling to room temperature, dichloromethane extraction, gets organic phase, is washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product, is 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, 2-(3' is obtained after drying, 4', 5'-trifluorophenyl)-5-methoxy pyrimidine 1.08g, yield is 45.0%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 240.0 (M ⁺)

Ultimate analysis: C11H7F3N2O

Theoretical value: C, 55.01; H, 2.94; F, 23.73; N, 11.66; O, 6.66;

Measured value: C, 55.07; H, 2.88; F, 23.69; N, 11.73; O, 6.63.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine

In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.48g (2mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine containing iridium dichloro dipolymer 0.33g, yield is 46.7%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In nitrogen atmosphere, be 2-(3' by 0.71g (0.5mmol) part, 4', 5'-trifluorophenyl)-5-methoxy pyrimidine containing iridium dichloro dipolymer, 0.35g (1.25mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.27g (5mmol) sodium methylate are dissolved in 25mL1, in 2-ethylene dichloride, stirring heating is warming up to 84 DEG C of 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, solid is had to separate out, filter, collect solid, solid uses deionized water, methanol wash for several times successively, solid after washing obtains the two (2-(3' of 0.23g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluoromethyl phenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 24.2%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 950.1 (M ⁺)

Ultimate analysis: C33H17F12IrN6O2

Theoretical value: C, 41.73; H, 1.80; F, 24.00; Ir, 20.24; N, 8.85; O, 3.37;

Measured value: C, 41.78; H, 1.72; F, 24.06; Ir, 20.21; N, 8.84; O, 3.39.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium.

As shown in Figure 4, 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 469nm place, has an acromion at 500nm place simultaneously, and this blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C are described ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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=0.15, blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, the C of visible the present embodiment ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium and have higher luminous quantum efficiency.

Embodiment 6

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine

In nitrogen atmosphere, by 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 1.76g (10mmol) 3,4,5-trifluoro-benzene boric 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, and 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 1:7 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine 1.39g, yield is 44.8%.Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 310.1 (M ⁺)

Ultimate analysis: C16H17F3N2O

Theoretical value: C, 61.93; H, 5.52; F, 18.37; N, 9.03; O, 5.16;

Measured value: C, 61.96; H, 5.46; F, 18.41; N, 9.06; O, 5.11.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine

In nitrogen atmosphere, by 0.36g (1mmol) three hydrated iridium trichloride and 0.93g (3mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining part after drying is 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer 0.26g, yield is 30.7%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium

In nitrogen atmosphere, be 2-(3' by 0.68g (0.4mmol) part, 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine containing iridium dichloro dipolymer, 0.22g (0.8mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.34g (3.2mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol, and stirring heating is warming up to 135 DEG C of reflux state reaction 5h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, filter, collect solid, solid uses deionized water, washed with diethylether for several times successively, solid after washing obtains the two (2-(3' of 0.09g blue phosphorescent through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close complex of iridium, yield is 11.0%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 957.2 (M ⁺)

Ultimate analysis: C38H36F6IrN9O2

Theoretical value: C, 44.75; H, 2.67; F, 22.35; Ir, 18.85; N, 8.24; O, 3.14;

Measured value: C, 44.77; H, 2.61; F, 22.41; Ir, 18.80; N, 8.28; O, 3.13.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 510nm 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=0.10.

Embodiment 7

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of complex of iridium.

Blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) to close the structural formula of complex of iridium as follows:

(1) synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines

In nitrogen atmosphere, by 2.28g (5mmol) 2-bromo-5-eicosyl pyrimidine, 1.32g (7.5mmol) 3,4,5-trifluoro-benzene boric acid 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, and 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 is separated for elutriant carries out silica gel column chromatography to crude product with the mixed solvent of normal hexane with volume ratio, after drying, obtain 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines 0.58g, yield is 22.9%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 506.3 (M ⁺)

Ultimate analysis: C30H45F3N2O

Theoretical value: C, 71.11; H, 8.95; F, 11.25; N, 5.53; O, 3.16;

Measured value: C, 71.16; H, 8.87; F, 11.29; N, 5.47; O, 3.21.

The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines.

(2) part is the synthesis containing iridium dichloro dipolymer of 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines

In nitrogen atmosphere, by 0.18g (0.5mmol) three hydrated iridium trichloride and 1.01g (2mmol) 2-(3', 4', 5'-trifluorophenyl)-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, obtaining 0.08g part after drying is 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer, yield is 12.9%.

Concrete reaction formula is as follows:

(3) blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of complex of iridium

In nitrogen atmosphere, be 2-(3' by 0.74g (0.3mmol) part, 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dipolymer, 0.25g (0.9mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.50g (3.6mmol) salt of wormwood are dissolved in 30mL2-methyl cellosolve, and stirring heating is warming up to 100 DEG C of state of temperature reaction 6h.Reaction terminates, after reaction solution is chilled to room temperature naturally, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, filter, collect solid, solid uses deionized water, washed with diethylether for several times successively, solid after washing obtains the two (2-(3' of 0.06g pure blue phosphorescence through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium, yield is 6.7%.

Concrete reaction formula is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1482.7 (M ⁺)

Ultimate analysis: C71H93F12IrN6O2

Theoretical value: C, 57.51; H, 6.32; F, 15.38; Ir, 12.96; N, 5.67; O, 2.16;

Measured value: C, 57.56; H, 6.22; F, 15.44; Ir, 12.91; N, 5.73; O, 2.14.

The material that the above-mentioned reaction of above data acknowledgement obtains is blue phosphorescent two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 490nm place, has an acromion at 521nm 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 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-(3' of blue phosphorescent prepared by embodiment 1, 4', 5'-trifluorophenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 8.3%, and maximum lumen efficiency is 9.9lm/W.

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''-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-(3' of blue phosphorescent prepared by embodiment 5, 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) 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 5.8%, and maximum lumen efficiency is 6.6lm/W.

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 shielding gas atmosphere, for 1:1 ~ 1:1.5 by structural formula be in molar ratio pyrimidine derivatives and 3,4,5-trifluoro-benzene boric acid 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, described R is hydrogen, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20;

In 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 shielding gas atmosphere; 1:2 ~ 1:3 contains iridium chlorine bridge dipolymer and 2 by described in molar ratio; 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is dissolved in the 3rd solvent; add carbonate or sodium methylate; be heated with stirring to reflux state 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:

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 1:4 ~ 1:7 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, and after reaction solution is chilled to room temperature naturally, adds distilled water precipitating, filter, collect solid, described solid uses deionized water, washed with diethylether successively, and the solid after washing obtains blue phosphorescent iridium metal complex through the mixed solvent recrystallization of methylene dichloride and anhydrous methanol.

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.