CN104327831A - Red light organic electrophosphorescent material, preparation method thereof and organic electroluminescent device - Google Patents

Abstract

The invention discloses a blue light organic electrophosphorescent material, the structural formula of the material is shown as P, wherein R is hydrogen atom, C1-C20 alkyl or C1-C20 alkoxy. A blue light organic electrophosphorescent material Iridium metal matched-type complex is prepared from 2-(3 ', 5 '-difluoro-4'-cyano phenyl) pyrimidine as a ring metal ligand and tetra (1-pyrazole) boride as an assistant ligand, by introduction of alkyl or alkoxy chains into the pyrimidine ring of the ring metal ligand for chemical modification, the regulation of emitting color of the material is realized, and high color purity blue light phosphorescence emission can be obtained. The invention also provides a preparation method of the blue light organic electrophosphorescent material and application of the blue light organic electrophosphorescent material in an organic electroluminescent device.

Description

A kind of blue light organic phosphorescent electroluminescent materials and preparation method thereof and organic electroluminescence device

Technical field

The present invention relates to field of photovoltaic materials, be specifically related to a kind of blue light organic phosphorescent electroluminescent materials and preparation method thereof 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 (Alq3) for luminescent material, the high-quality thin film of even compact is made with aromatic diamine, obtain 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.And 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 emphasis that the efficiency improving blue light material has just become people to study with purity of color.

Holmes R J, the people such as Forrest S R are at App.Phys.Lett., 2003, two [2-(4' is disclosed in 82 (15): 2422-2424 articles, 6'-difluorophenyl) pyridine-N, C2'] (2-pyridinecarboxylic) close iridium (FIrpic), is that report is at most at present, also be the best blue light organic phosphorescent electroluminescent materials of over-all properties, structural formula is as follows:

Although people have carried out various optimization to FIrpic class OLED structure, device performance have also been obtained very large raising, but the maximum weakness of FIrpic is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED made is (0.13 ~ 0.17,0.29 ~ 0.39) change between, between this and standard blue light CIE (0.137,0.084), have very large gap.

2003, Holmes R J, the people such as Forrest S R disclose and change with four (1-pyrazoles) two [2-(4' of blue phosphorescent iridium metal complex luminescent material that boron is assistant ligand, 6'-difluorophenyl) pyridine-N, C2'] (four (1-pyrazoles) change boron) close iridium (FIr6) (App.Phys.Lett., 2003, 83:3818-3820.), the CIE being entrained in the OLED in the wide energy gap material of main part of high triplet UGH1 or UGH2 is (0.16, 0.26), with (0.16 of the FIrpic device of identity unit structure, 0.37) compare, blue light color purity is improved.The introducing blue shift emission wavelength of material effectively that high field intensity assistant ligand four (1-pyrazoles) changes boron, blue light color purity is higher, becomes one of first-selected assistant ligand of different distribution type blue phosphorescent complex of iridium luminescent material.

The Jun Yeob Lee teach problem group of Tan Guo university of Korea S in 2008 reports a kind of novel blue light phosphor material-tri-(2-(4' rolled into a ball by strong electron-withdrawing group in cyano group introducing ring master metal part, the fluoro-5'-cyano-phenyl of 6'-bis-) pyridine-N, C2') iridium (FCNIr) is closed, the maximum emission wavelength of its blue emitting phosphor device PHOLEDs made is blue shifted to 453nm, purity of color CIEx, y is also increased to (0.15,0.19).Within 2011, Jun Yeob Lee teach problem group reports blue emitting phosphor material-bis-(2-(4' of cyano-containing in another ring master metal part in succession, the fluoro-5'-cyano-phenyl of 6'-bis-) pyridine-N, C2') (2-pyridinecarboxylic) closes iridium (FCNIrpic) excellent properties in blue light and white light parts, by optimised devices structure, the maximum emission wavelength of FCNIrpic blue-light device is blue shifted to 457 ~ 462nm, purity of color CIEx, y is also increased to (0.14 ~ 0.18,0.17 ~ 0.25).Facts have proved, in the main part of phosphor material complex of iridium, introduce strong electron-withdrawing substituent-cyano group becomes one of effective ways obtaining novel blue light with high color purity phosphor material.

The research of people to organic electromechanical phosphorescent material iridium metal complex is being goed deep into always, but there is bottleneck problem in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Therefore, the blue phosphorescent organic electroluminescent material developing high color purity becomes the megatrend expanding blue light material research field.

Summary of the invention

Based on the problems referred to above, the invention provides a kind of blue-ray organic electroluminescent material, this material has good blue light luminous efficiency and good processing characteristics.Present invention also offers the preparation method of this blue-ray organic electroluminescent material and the application in organic electroluminescence device thereof.

First aspect, the invention provides a kind of blue light organic phosphorescent electroluminescent materials, and its general structure is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

Second aspect, the invention provides a kind of preparation method of blue light organic phosphorescent electroluminescent materials, comprises the steps:

(1), under protective gas existent condition, by structural formula be compd A and structural formula be compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1 ~ 1:1.5; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group;

(2), under protective gas existent condition, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 24h; Be cooled to room temperature, separating-purifying, obtaining structural formula is chlorine bridge dipolymer; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group;

(3) under protective gas existent condition; described chlorine bridge dipolymer to be dissolved in after the second organic solvent with the methanol solution of trifluoroacetic acid silver according to the mol ratio of 1:1.6 ~ 1:3 at room temperature after mix and blend 2 ~ 3h, the centrifugal settled solution obtained is steamed to desolventize through over-rotation to obtain residue.And then, under protective gas existent condition, above-mentioned residue and structural formula are compound C be dissolved in proportion in acetonitrile, carry out ligand exchange reaction 24h under reflux state, be cooled to room temperature, separating-purifying, obtaining structural formula is blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

Preferably, described first organic solvent is toluene or dimethyl formamide (DMF).

Preferably, described alkali is sodium carbonate (Na ₂cO ₃) or salt of wormwood (K ₂cO ₃), the mol ratio of described alkali and compd A is 1:1 ~ 3:1.

Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh ₃) ₄) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh ₃) ₂cl ₂), the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.

Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.

Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of described three hydrated iridium trichloride is 0.04 ~ 0.05mol/L.

Preferably, the volume ratio of described cellosolvo and water is 3:1.

Preferably, described second organic solvent is trichloromethane or methylene dichloride.

Preferably, the mol ratio of described chlorine bridge dimer and Compound C is 1:1.6 ~ 1:3.

Preferably, the concentration range of described chlorine bridge dipolymer in solvent acetonitrile is 0.01 ~ 0.025mol/L.

Preferably, the separating-purifying of described cyclic metal complexes comprises:

After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.

More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:5 ~ 1:10.

Preferably, described protective gas is nitrogen, argon gas or helium.

Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:

After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.

Preferably, the separating-purifying of described blue light organic phosphorescent electroluminescent materials comprises:

Question response stops being cooled to room temperature, and filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, after the mixed solution recrystallization that methyl alcohol and methylene dichloride are formed, obtain described blue light organic phosphorescent electroluminescent materials.

This kind of blue light organic phosphorescent electroluminescent materials feature provided by the invention is to be cyclic metal complexes agent structure with 2-(3', 5'-bis-fluoro-4'-cyano-phenyl) pyrimidine, to change with four (1-pyrazoles) the different distribution type metal iridium complex that boron is assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and cyano group are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The difference electron-donating group alkyl of the straight or branched formula of different lengths or alkoxyl group being introduced pyrimidine ring replaces on position, not only can increase material solubleness in organic solvent, and on pyrimidine ring, produce space steric effect to reduce the self-quenching phenomenon of triplet exciton in solid-state, stronger electronic effect of giving can also make the further blue shift of the emission wavelength of material, thus obtains higher luminous efficiency and blue light emitting wavelength; In addition, the introducing that on phenyl ring, strong electron-withdrawing group fluorine-based, the cyano group of group and assistant ligand four (1-pyrazoles) change boron can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.

The third aspect, the invention provides a kind of organic electroluminescence device, comprises luminescent layer, and adulterate in described luminescent layer blue light organic phosphorescent electroluminescent materials, and its general structure is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching high purity blue light and good device performance.

Accompanying drawing explanation

Fig. 1 is the preparation flow schematic diagram of the blue light organic phosphorescent electroluminescent materials of an embodiment;

Fig. 2 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials obtained in embodiment 1;

Fig. 3 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials obtained in embodiment 5;

Fig. 4 is the structural representation of organic electroluminescence device obtained in Application Example.

Embodiment

Blue light organic phosphorescent electroluminescent materials provided by the invention, with 2-(3', the fluoro-4'-cyano-phenyl of 5'-bis-) pyrimidine is cyclic metal complexes, boron is changed for assistant ligand with four (1-pyrazoles), synthesize a kind of blue light organic phosphorescent electroluminescent materials iridium metals with distribution type title complex, and realize the adjustment to material emission color by the chemically modified introducing alkyl or oxyalkyl chain on the pyrimidine ring of cyclic metal complexes, thus obtain the higher phosphorescent emissions performance of blue light color purity.

The general structure of blue light organic phosphorescent electroluminescent materials provided by the invention is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group, the structural formula of described cyclic metal complexes is:

Fig. 1 is the preparation flow schematic diagram of the blue light organic phosphorescent electroluminescent materials of an embodiment.Refer to Fig. 1, the preparation method of above-mentioned blue light organic phosphorescent electroluminescent materials, comprises the steps:

Under S1, protective gas existent condition, by structural formula be compd A and structural formula be compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1 ~ 1:1.5; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group; Reaction formula is:

Under S2, protective gas existent condition, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 24h; Be cooled to room temperature, separating-purifying, obtaining structural formula is chlorine bridge dipolymer; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group; Reaction formula is:

Under S3, protective gas existent condition; described chlorine bridge dipolymer to be dissolved in after the second organic solvent with the methanol solution of trifluoroacetic acid silver according to the mol ratio of 1:1.6 ~ 1:3 at room temperature after mix and blend 2 ~ 3h, the centrifugal settled solution obtained is steamed to desolventize through over-rotation to obtain residue.And then, under protective gas existent condition, above-mentioned residue and structural formula are compound C be dissolved in proportion in acetonitrile, carry out ligand exchange reaction 24h under reflux state, be cooled to room temperature, separating-purifying, obtaining structural formula is blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group; Reaction formula is:

Preferably, described first organic solvent is toluene or dimethyl formamide (DMF).

Preferably, described alkali is sodium carbonate (Na ₂cO ₃) or salt of wormwood (K ₂cO ₃), the mol ratio of described alkali and compd A is 1:1 ~ 3:1.

Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh ₃) ₄) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh ₃) ₂cl ₂), the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.

Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.

Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of described three hydrated iridium trichloride is 0.04 ~ 0.05mol/L.

Preferably, the volume ratio of described cellosolvo and water is 3:1.

Preferably, described second organic solvent is trichloromethane or methylene dichloride.

Preferably, the mol ratio of described chlorine bridge dimer and Compound C is 1:1.6 ~ 1:3.

Preferably, the concentration range of described chlorine bridge dipolymer in solvent acetonitrile is 0.01 ~ 0.025mol/L.

Preferably, the separating-purifying of described cyclic metal complexes comprises:

After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.

More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:5 ~ 1:10.

Preferably, described rare gas element is nitrogen.

Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:

After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.

Preferably, the separating-purifying of described blue light organic phosphorescent electroluminescent materials comprises:

Question response stops being cooled to room temperature, and filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, after the mixed solution recrystallization that methyl alcohol and methylene dichloride are formed, obtain described blue light organic phosphorescent electroluminescent materials.

This kind of blue light organic phosphorescent electroluminescent materials feature provided by the invention is to be cyclic metal complexes agent structure with 2-(3', 5'-bis-fluoro-4'-cyano-phenyl) pyrimidine, to change with four (1-pyrazoles) the different distribution type metal iridium complex that boron is assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and cyano group are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The difference electron-donating group alkyl of the straight or branched formula of different lengths or alkoxyl group being introduced pyrimidine ring replaces on position, not only can increase material solubleness in organic solvent, and on pyrimidine ring, produce space steric effect to reduce the self-quenching phenomenon of triplet exciton in solid-state, stronger electronic effect of giving can also make the further blue shift of the emission wavelength of material, thus obtains higher luminous efficiency and blue light emitting wavelength; In addition, the introducing that on phenyl ring, strong electron-withdrawing group fluorine-based, the cyano group of group and assistant ligand four (1-pyrazoles) change boron can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.

A kind of organic electroluminescence device, comprise luminescent layer, doped with blue light organic phosphorescent electroluminescent materials in described luminescent layer, its general structure is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching high purity blue light and good device performance.

Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.

Embodiment 1: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

(1) synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-) pyrimidine

Under nitrogen protection; 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.20g (12mmol) 3; the fluoro-4-cyanophenylboronic acid of 5-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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/10 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.06g, yield is 48.8%.

Structural Identification:

Mass spectrum (MS m/z): 217.0 (M+)

Ultimate analysis: C ₁₁h ₅f ₂n ₃

Theoretical value: C, 60.83; H, 2.32; F, 17.50; N, 19.35;

Measured value: C, 60.87; H, 2.25; F, 17.57; N, 19.31.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl) pyrimidine containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride; 0.54g (2.5mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to pyrimidine, is heated to stirring reaction 24h under reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.37g after drying, yield is 56.1%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.66g (0.5mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) pyrimidine be dissolved in 25mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 25mL containing 0.24g (1.1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 2h.Whizzer obtains settled solution after separating AgCl precipitation, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.48g (1.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, are heated to back flow reaction 24h at 81 DEG C of temperature.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.17g, and productive rate is 18.8%.

Structural Identification:

Mass spectrum (MS m/z): 904.2 (M+)

Ultimate analysis: C ₃₄h ₂₀bF ₄irN ₁₄

Theoretical value: C, 45.19; H, 2.23; B, 1.20; F, 8.41; Ir, 21.27; N, 21.70;

Measured value: C, 45.25; H, 2.17; B, 1.24; F, 8.36; Ir, 21.33; N, 21.65.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium.

Fig. 2 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials obtained in embodiment 1.As shown in Figure 2, 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 455nm place, has an acromion at 479nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.

In addition, 10 ^-6the CH of M end product ₂cl ₂solution at 298K temperature, with concentration for ~ 10 ^-6the CH of the FIrpic of M ₂cl ₂solution is standard (Φ PL=0.26), records the Φ PL=0.28 of end product, and the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.

Embodiment 2: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

(1) synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methylpyrimidine

Under nitrogen protection; the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 1.83g (10mmol) 3; the fluoro-4-cyanophenylboronic acid of 5-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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.88g, yield is 38.1%.

Structural Identification:

Mass spectrum (MS m/z): 231.1 (M+)

Ultimate analysis: C ₁₂h ₇f ₂n ₃

Theoretical value: C, 62.34; H, 3.05; F, 16.43; N, 18.17;

Measured value: C, 62.38; H, 3.01; F, 16.49; N, 18.12.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride; 0.46g (2mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-methylpyrimidine, is heated to stirring reaction 24h under reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.28g after drying, yield is 40.7%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.69g (0.5mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-5-methylpyrimidine be dissolved in 20mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.40g (1.25mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.14g, and productive rate is 15.0%.

Structural Identification:

Mass spectrum (MS m/z): 932.2 (M+)

Ultimate analysis: C ₃₆h ₂₄bF ₄irN ₁₄

Theoretical value: C, 46.41; H, 2.60; B, 1.16; F, 8.16; Ir, 20.63; N, 21.05;

Measured value: C, 46.47; H, 2.55; B, 1.12; F, 8.22; Ir, 20.56; N, 21.08.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium.

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, with the CH of the FIrpic of same concentrations simultaneously ₂cl ₂solution is standard (Φ PL=0.26), record the Φ PL=0.12 of end product, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.

Embodiment 3: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-t-butyl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

(1) synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-t-butyl pyrimidines

Under nitrogen protection; the bromo-5-t-butyl pyrimidines of 2.15g (10mmol) 2-, 2.56g (14mmol) 3; 5-bis-fluoro-4-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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/6 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.82g, yield is 30.0%.

Structural Identification:

Mass spectrum (MS m/z): 273.1 (M+)

Ultimate analysis: C ₁₅h ₁₃f ₂n ₃

Theoretical value: C, 65.93; H, 4.79; F, 13.90; N, 15.38;

Measured value: C, 65.87; H, 4.84; F, 13.93; N, 15.36.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride and 0.82g (3mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-t-butyl pyrimidines, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.25g after drying, yield is 32.4%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-t-butyl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.77g (0.5mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-5-t-butyl pyrimidines be dissolved in 25mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 25mL containing 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.25g (0.8mmol) four (1-pyrazoles) boronation potassium are dissolved in 25mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.10g, and productive rate is 9.8%.

Structural Identification:

Mass spectrum (MS m/z): 1016.3 (M+)

Ultimate analysis: C ₄₂h ₃₆bF ₄irN ₁₄

Theoretical value: C, 49.66; H, 3.57; B, 1.06; F, 7.48; Ir, 18.92; N, 19.30;

Measured value: C, 49.62; H, 3.65; B, 1.01; F, 7.56; Ir, 18.87; N, 19.29.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-t-butyl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 461nm place, has an acromion at 487nm place, with the CH of the FIrpic of same concentrations simultaneously ₂cl ₂solution is standard (Φ PL=0.26), records the Φ PL=0.20 of end product.

Embodiment 4: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-eicosyl pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

(1) synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-eicosyl pyrimidine

Under nitrogen protection; 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.37g (7.5mmol) 3; the fluoro-4-cyanophenylboronic acid of 5-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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.45g, yield is 18.1%.

Structural Identification:

Mass spectrum (MS m/z): 497.4 (M+)

Ultimate analysis: C ₃₁h ₄₅f ₂n ₃

Theoretical value: C, 74.81; H, 9.11; F, 7.63; N, 8.44;

Measured value: C, 74.87; H, 9.03; F, 7.68; N, 8.42.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.18g (0.5mmol) three hydrated iridium trichloride; 0.99g (2mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 10mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-eicosyl pyrimidine, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.09g after drying, yield is 14.7%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-eicosyl pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.49g (0.2mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-4-eicosyl pyrimidine be dissolved in 15mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 15mL containing 0.13g (0.6mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.16g (0.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.04g, and productive rate is 6.8%.

Structural Identification:

Mass spectrum (MS m/z): 1464.8 (M+)

Ultimate analysis: C ₇₄h ₁₀₀bF ₄irN ₁₄

Theoretical value: C, 60.68; H, 6.88; B, 0.74; F, 5.19; Ir, 13.12; N, 13.39;

Measured value: C, 60.64; H, 6.95; B, 0.70; F, 5.24; Ir, 13.06; N, 13.41.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-eicosyl pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 480nm 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), records the Φ PL=0.06 of end product.

Embodiment 5: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methoxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

The synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methoxy pyrimidine

Under nitrogen protection; the bromo-5-methoxy pyrimidine of 1.89g (10mmol) 2-, 2.20g (12mmol) 3; the fluoro-4-cyanophenylboronic acid of 5-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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/7 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.91g, yield is 36.8%.

Structural Identification:

Mass spectrum (MS m/z): 247.1 (M+)

Ultimate analysis: C ₁₂h ₇f ₂n ₃o

Theoretical value: C, 58.30; H, 2.85; F, 15.37; N, 17.00; O, 6.47;

Measured value: C, 58.36; H, 2.77; F, 15.40; N, 17.04; O, 6.43.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride; 0.49g (2mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-methoxy pyrimidine, is heated to stirring reaction 24h under reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.25g after drying, yield is 34.7%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methoxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.72g (0.5mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-5-methoxy pyrimidine be dissolved in 20mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing 0.24g (1.1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.48g (1.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.13g, and productive rate is 13.5%.

Structural Identification:

Mass spectrum (MS m/z): 964.2 (M+)

Ultimate analysis: C ₃₆h ₂₄bF ₄irN ₁₄o ₂

Theoretical value: C, 44.87; H, 2.51; B, 1.12; F, 7.89; Ir, 19.95; N, 20.35; O, 3.32;

Measured value: C, 44.83; H, 2.58; B, 1.06; F, 7.95; Ir, 19.90; N, 20.38; O, 3.30.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-methoxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium.

Fig. 3 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials obtained in embodiment 5.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 455nm place, has an acromion at 479nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.

In addition, 10 ^-6the CH of M end product ₂cl ₂solution at 298K temperature, with concentration for ~ 10 ^-6the CH of the FIrpic of M ₂cl ₂solution is standard (Φ PL=0.26), records the Φ PL=0.13 of end product, and the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.

Embodiment 6: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-hexyloxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

The synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-hexyloxy pyrimidine

Under nitrogen protection; 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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/10 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.92g, yield is 29.0%.

Structural Identification:

Mass spectrum (MS m/z): 317.1 (M+)

Ultimate analysis: C ₁₇h ₁₇f ₂n ₃o

Theoretical value: C, 64.34; H, 5.40; F, 11.97; N, 13.24; O, 5.04;

Measured value: C, 64.39; H, 5.33; F, 12.04; N, 13.26; O, 4.98.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.36g (1mmol) three hydrated iridium trichloride and 0.95g (3mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 25mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-hexyloxy pyrimidine, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.22g after drying, yield is 25.6%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-hexyloxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.86g (0.5mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-4-hexyloxy pyrimidine be dissolved in 20mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.32g (1mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.10g, and productive rate is 9.0%.

Structural Identification:

Mass spectrum (MS m/z): 1104.3 (M+)

Ultimate analysis: C ₄₆h ₄₄bF ₄irN ₁₄o ₂

Theoretical value: C, 50.05; H, 4.02; B, 0.98; F, 6.88; Ir, 17.41; N, 17.76; O, 2.90;

Measured value: C, 50.13; H, 3.97; B, 0.94; F, 6.95; Ir, 17.34; N, 17.75; O, 2.92.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-4-hexyloxy pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes 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), records the Φ PL=0.08 of end product.

Embodiment 7: title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-eicosane oxygen yl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

The synthesis of 2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-eicosane oxygen yl pyrimidines

Under nitrogen protection; 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.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.46g, yield is 17.9%.

Structural Identification:

Mass spectrum (MS m/z): 513.3 (M+)

Ultimate analysis: C ₃₁h ₄₅f ₂n ₃o

Theoretical value: C, 72.48; H, 8.83; F, 7.40; N, 8.18; O, 3.11;

Measured value: C, 72.43; H, 8.89; F, 7.34; N, 8.26; O, 3.08.

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

(2) part be 2-(3', 5'-bis-fluoro-4'-cyano-phenyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro

Under nitrogen protection; 0.18g (0.5mmol) three hydrated iridium trichloride; 1.03g (2mmol) 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-) to be dissolved in 10mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-eicosane oxygen yl pyrimidines, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.08g after drying, yield is 12.8%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-eicosane oxygen yl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes the synthesis of iridium

Under nitrogen protection; 0.50g (0.2mmol) part is 2-(3'; the fluoro-4'-cyano-phenyl of 5'-bis-)-5-eicosane oxygen yl pyrimidines be dissolved in 15mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 15mL containing 0.13g (0.6mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.The settled solution after AgCl precipitation separated by whizzer, rotates steaming and desolventizes.Under nitrogen protection, residue and 0.14g (0.44mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Be chilled to room temperature, filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.02g, and productive rate is 3.3%.

Structural Identification:

Mass spectrum (MS m/z): 1496.8 (M+)

Ultimate analysis: C ₇₄h ₁₀₀bF ₄irN ₁₄o ₂

Theoretical value: C, 59.38; H, 6.73; B, 0.72; F, 5.08; Ir, 12.84; N, 13.10; O, 2.14;

Measured value: C, 59.46; H, 6.63; B, 0.77; F, 5.02; Ir, 12.90; N, 13.14; O, 2.08.

The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two (2-(the fluoro-4'-cyano-phenyl of 3', 5'-bis-)-5-eicosane oxygen yl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-6the maximum emission peak of the emmission spectrum M), at 483nm place, has an acromion at 509nm place, with the CH of the FIrpic of same concentrations simultaneously ₂cl ₂solution is standard (Φ PL=0.26), records the Φ PL=0.03 of end product.

Embodiment 8:

Fig. 4 is the structural representation of organic electroluminescence device obtained in Application Example.With the two (2-(3' of the title complex that embodiment 1 is obtained, the fluoro-4'-cyano-phenyl of 5'-bis-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) close iridium as luminescent layer doping object organic electroluminescence device, structure as shown in Figure 4:

This device is followed successively by ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%Ir title complex (30nm)/BCP (10nm)/Alq3 (35nm)/LiF (1nm)/Al (120nm), namely on a glass-based plate, depositing a layer thickness is 200nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 301, on anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, two (1-the naphthyl)-N of N'-, N'-diphenylbenzidine) hole mobile material is as hole transmission layer 303, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is as electronic barrier layer 304, with the two (2-(3' prepared doped with 7wt% embodiment 1 that a layer thickness is 30nm, the fluoro-4'-cyano-phenyl of 5'-bis-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes the mCP of iridium as luminescent layer 305, on this luminescent layer 305, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 306, thickness is that the Alq3 (three (oxine) aluminium) of 35nm is as electron transfer layer 307, thickness is that the LiF of 1nm is as electron injection buffer layer 308, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metal A l of 120nm, as the negative electrode 309 of device.

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 9.8%, and maximum current efficiency is 10.5cd/A.

Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. a blue light organic phosphorescent electroluminescent materials, is characterized in that, the general structure of described blue light organic phosphorescent electroluminescent materials is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

2. a preparation method for blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:

(1), under protective gas existent condition, by structural formula be compd A and structural formula be compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1 ~ 1:1.5; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group;

(2), under protective gas existent condition, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 24h; Be cooled to room temperature, separating-purifying, obtaining structural formula is chlorine bridge dipolymer; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group;

(3) under protective gas existent condition; described chlorine bridge dipolymer to be dissolved in after the second organic solvent with the methanol solution of trifluoroacetic acid silver according to the mol ratio of 1:1.6 ~ 1:3 at room temperature after mix and blend 2 ~ 3h, the centrifugal settled solution obtained is steamed to desolventize through over-rotation to obtain residue.And then, under protective gas existent condition, above-mentioned residue and structural formula are compound C be dissolved in proportion in acetonitrile, carry out ligand exchange reaction 24h under reflux state, be cooled to room temperature, separating-purifying, obtaining structural formula is blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.

3. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the mol ratio of described alkali and compd A is 1:1 ~ 3:1.

4. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, it is characterized in that, described catalyzer is that four (triphenylphosphines) close palladium or dichloro two (triphenyl phosphorus) closes palladium, and the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.

5. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.

6. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the concentration range of described chlorine bridge dimer in solvent acetonitrile is 0.01 ~ 0.025mol/L.

7. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described cyclic metal complexes comprises:

After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.

8. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described chlorine bridge dipolymer comprises:

After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.

9. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described blue light organic phosphorescent electroluminescent materials comprises:

Question response stops being cooled to room temperature, and filter, filter residue q. s. methylene chloride washs, merging filtrate, rotates steaming and desolventizes, obtain crude product.Crude product uses methyl alcohol, deionized water wash successively, after the mixed solution recrystallization that methyl alcohol and methylene dichloride are formed, obtain described blue light organic phosphorescent electroluminescent materials.

10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, doped with blue light organic phosphorescent electroluminescent materials in described luminescent layer, described blue light organic phosphorescent electroluminescent materials general structure is as shown in P:

Wherein, R is hydrogen atom, C ₁~ C ₂₀alkyl or alkoxyl group.