CN104560024A - Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device - Google Patents

Abstract

The invention provides an organic electroluminescent material, a preparation method of the organic electroluminescent material and an organic electroluminescent device. The organic electroluminescent material has a general formula (P) as shown in the specification, wherein R1 is hydrogen atom, C1-20 linear alkyl, C1-20 branched alkyl, C1-20 linear alkoxy or C1-20 branched alkoxy; and R2 is hydrogen atom or tertiary butyl. According to the organic electroluminescent material, 2-(4',6'-difluoro-5'-trifluoromethylphenyl) pyrimidine serving as a cyclometalated ligand and 3-trifluoromethyl-5-(pyridine-2'-yl)pyridine or 3-trifluoromethyl-5-(4-tert-butylpyridine-2-yl)pyridine serving as an auxiliary ligand are adopted to synthesize a blue-light organic electroluminescent material iridium heterotropic complex, and the illuminating color of the material is adjusted through chemical modification performed by introducing alkyl or alkoxy chain on the pyrimidine ring of the cyclometalated ligand, so that phosphorescence emission having high luminescence efficiency can be obtained.

Description

Electroluminescent organic material and preparation method thereof and organic electroluminescence device

Technical field

The present invention relates to phosphor material field, particularly relate to a kind of electroluminescent organic material.The invention still further relates to the preparation method of this electroluminescent organic material and its application in 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.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 breakthrough point that the efficiency improving blue light material has just become people to study with purity of color.

The people such as Holmes R J, Forrest S R, at App.Phys.Lett., disclose two [2-(4', 6'-difluorophenyl) pyridine-N, C in 2003,82 (15): 2422-2424 articles ₂'] (2-pyridinecarboxylic) close iridium [FIrpic], be at present report at most, be also the best blue-ray organic electroluminescent material 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.

After FIrpic, a series of different distribution type complex of iridium blue phosphor materials with the strong assistant ligand of high field is developed.2012, the people such as the Cheng-Han Yang of Munster, Germany university are at Chem.Mater.2012, reporting a series of in 24,3684-3695 literary composition take 3-trifluoromethyl-5-(pyridine-2'-base) pyrazoles or 3-trifluoromethyl-5-(4'-tert .-butylpyridine-2'-base) pyrazoles as the blue phosphorescent complex of iridium luminescent material of assistant ligand.No matter all materials are at room temperature in the solution or all show efficient real blue phosphorescent under filminess, maximum emission wavelength is all about 440nm, and phosphorescence quantum yield is respectively 0.77 ~ 0.87 and 0.62 ~ 0.93.Therefore, the introducing of high field strong assistant ligand 3-trifluoromethyl-5-(pyridine-2'-base) pyrazoles or 3-trifluoromethyl-5-(4'-tert .-butylpyridine-2'-base) pyrazoles can the blue shift emission wavelength of material effectively, blue light color purity is higher, becomes one of assistant ligand of different distribution type blue phosphorescent complex of iridium luminescent material.

2009, the people such as the Youngjin Kang of Korea S report a kind of dipyridyl be cyclic metal complexes agent structure containing complex of iridium blue phosphor materials-tri-(fluoro-2, the 3'-dipyridyl-N of 2', 6'-bis-, C ₄') close iridium Ir (dfpypy) ₃[Inorg.Chem.2009,48,1030-1037.], because directly employing atom N replaces the CH on phenyl ring, the electronegativity of N is better than C, causes the HOMO energy level of material to decline further, emission wavelength blue shift.Its CH ₂cl ₂solution maximum emission wavelength at room temperature reaches 438nm, phosphorescence quantum yield Φ _pLreach 0.71, chromaticity coordinates value CIE is (0.14,0.12), the equal <0.15 of x, y value.The CH adopting N to replace on phenyl ring in main part becomes the effective ways obtaining novel blue light with high color purity phosphor material.

The research of people to electroluminescent organic 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

The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of electroluminescent organic material and preparation method thereof and organic electroluminescence device are provided.

The invention provides the electroluminescent organic material with following general formula (P):

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy; R ₂for hydrogen atom or the tertiary butyl.

Described R ₁be positioned 4-or the 5-position of its place pyrimidine.

The present invention also provides the preparation method of above-mentioned electroluminescent organic material, and the method comprises the following steps:

E () provides following compd A and compd B:

Described compd A is described compd B is

F () is under atmosphere of inert gases, adding by volume ratio by described compd A and described compd B according to the mol ratio of 1:2.5 ~ 1:4 is in the mixed solvent that forms of the reaction solvent of 3:1 and ethanol, ligand exchange reaction is carried out under reflux temperature, separating-purifying reaction solution, obtains the electroluminescent organic material of following general formula (P):

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy; R ₂for hydrogen atom or the tertiary butyl.

In step (b), described reaction solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.

In step (b), the concentration range of described compd A in described mixed solvent is 0.01 ~ 0.0167mol/L.Described compd A adopts following steps to obtain:

C () provides following Compound C and Compound D:

Described Compound C is described Compound D is IrCl ₃3H ₂o, i.e. three hydrated iridium trichloride,

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy;

D () is under atmosphere of inert gases, described Compound C and described Compound D are added in the cellosolvo aqueous solution according to the mol ratio of 2.2:1 ~ 3:1, the volume ratio of cellosolvo and water is 3:1, the concentration range of wherein said Compound D in the described cellosolvo aqueous solution is 0.02 ~ 0.05mol/L, be heated to stirring reaction 22 ~ 25h under reflux state, obtain described compd A.

Described Compound C adopts following steps to obtain:

A () provides following compd E and compound F 17-hydroxy-corticosterone;

Described compd E is described compound F 17-hydroxy-corticosterone is i.e. 2,4-bis-fluoro-3-trifluoromethylbenzene boronic acid,

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy.

B () is under atmosphere of inert gases, be that described compd E and the described compound F 17-hydroxy-corticosterone of 1:1 ~ 1:1.5 is dissolved in organic solvent by palladium catalyst and mol ratio, then drip alkaline solution and reheat Suzuki linked reaction 6 ~ 12h to 85 ~ 100 DEG C of temperature, after being cooled to room temperature, separating-purifying reaction solution, obtains described Compound C.

Described palladium catalyst closes palladium for two chlorine two (triphenyl phosphorus) or four (triphenyl phosphorus) close palladium, and described alkaline solution is solution of potassium carbonate or sodium carbonate solution, and described organic solvent is toluene solution or DMF solution.

The mol ratio of described palladium catalyst and described compd E is 0.03 ~ 0.05:1; Alkali solute in described alkaline solution and the mol ratio of described compd E are 1 ~ 3:1.

The present invention also proposes a kind of organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, and the material of described luminescent layer is above-mentioned electroluminescent organic material.

Compared with prior art, there is following advantage in electroluminescent organic material of the present invention and preparation method thereof and organic electroluminescence device:

This electroluminescent organic material is cyclic metal complexes agent structure with 2-(4', 6'-bis-fluoro-5'-trifluoromethyl) pyrimidine, take 3-trifluoromethyl-5-(pyridine-2-base) pyrazoles or 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles as the different distribution type metal iridium complex of 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 trifluoromethyl are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and branch chain type alkyl or alkoxyl group can produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; In addition, on phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 3-trifluoromethyl-5-(pyridine-2-base) pyrazoles or 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles can also improve luminescent properties, be beneficial to evaporation, increase film-forming type and improve the stability of device.

Accompanying drawing explanation

Fig. 1 is the synthesis general line figure of electroluminescent organic material of the present invention.

Fig. 2 be in embodiment 1 electroluminescent organic material synthetic route chart.

Fig. 3 is the structural representation of organic electroluminescence device in embodiment 4.

Fig. 4 is the utilizing emitted light spectrogram of electroluminescent organic material in embodiment 1.

Embodiment

Below in conjunction with embodiment, elaboration is further given to the present invention.

Electroluminescent organic material of the present invention has following general formula:

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy; R ₂for hydrogen atom or the tertiary butyl; Described R ₁be positioned the 4-of its place pyrimidine, 5-position.

The preparation process of electroluminescent organic material of the present invention (P) is roughly divided into following steps:

(1) make compd E and compound F 17-hydroxy-corticosterone by Suzuki linked reaction synthetic compound C; Wherein, compound F 17-hydroxy-corticosterone is the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-, and the structural formula of compd E and Compound C is as follows:

Compd E is compound C is wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy.

(2) Compound C step (1) obtained and Compound D are reacted and are generated chlorine bridge dipolymer, i.e. compd A.Wherein, Compound D is three hydrated iridium trichloride IrCl ₃3H ₂o.The structural formula of compd A is as follows:

(3) compd A obtained for step (2) being used as cyclic metal complexes, compd B being used as assistant ligand source, making compd A and compd B react to obtain iridium metal complex, is also electroluminescent organic material (P).The structural formula of compd B is as follows:

With embodiment, electroluminescent organic material of the present invention and preparation method thereof and organic electroluminescence device are specifically described below:

Embodiment 1: electroluminescent organic material disclosed in the present embodiment (P) is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

(1) the building-up reactions formula of 2-(2', 4'-bis-fluoro-3'-trifluoromethyl) pyrimidine is as follows:

Concrete steps are: under nitrogen atmosphere, 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.71g (12mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40ml toluene, stir 10min.The aqueous solution of 20ml containing 2.76g (20mmol) salt of wormwood is dripped 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 1/4 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 40.0%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 260.0 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₁h ₅f ₅n ₂.Theoretical value: C, 50.78; H, 1.94; F, 36.51; N, 10.77; Measured value: C, 50.73; H, 1.97; F, 36.56; N, 10.74.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-) pyrimidine.

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.71g (2mmol) three hydrated iridium trichloride and 1.82g (7mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) to be dissolved in 60ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to pyrimidine, is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.92g, yield is 61.7%.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the synthesis of iridium

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.75g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) pyrimidine to be dissolved in 30ml volume ratio containing iridium dichloro dimer and 0.32g (1.5mmol) 3-trifluoromethyl-5-(pyridine-2-base) pyrazoles be in the methylene dichloride of 3:1 and the mixing solutions of ethanol, under being heated to 60 DEG C of states, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.60g, yield is 65.0%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z): 923.1 (M ⁺); Its ultimate analysis is: C ₃₁h ₁₃f ₁₃irN ₇, theoretical value: C, 40.35; H, 1.42; F, 26.77; Ir, 20.83; N, 10.63; Measured value: C, 40.30; H, 1.48; F, 26.73; Ir, 20.88; N, 10.61.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ²') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium, is namely electroluminescent organic material (P).

As shown in Figure 4, transverse axis is luminous (unit nm), and the longitudinal axis is normalized photoluminescence intensity, and end product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 456nm place, has a peak at 485nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.

In addition, 10 ^-5the CH of M end product ₂cl ₂solution at 298K temperature, with concentration for ~ 10 ^-5the Ir (ppy) of M ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.27, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.

Embodiment 2: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

It adopts following steps to obtain:

(1) synthesis of 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-) pyrimidine

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.71g (12mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40ml toluene, stir 10min.The aqueous solution of 20ml containing 2.76g (20mmol) salt of wormwood is dripped 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 1/4 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 40.0%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 260.0 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₁h ₅f ₅n ₂, theoretical value: C, 50.78; H, 1.94; F, 36.51; N, 10.77; Measured value: C, 50.73; H, 1.97; F, 36.56; N, 10.74.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-) pyrimidine.

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.71g (2mmol) three hydrated iridium trichloride and 1.82g (7mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) to be dissolved in 60ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to pyrimidine, is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.92g, yield is 61.7%.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close the synthesis of iridium

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.75g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) pyrimidine to be dissolved in 30ml volume ratio containing iridium dichloro dimer and 0.40g (1.5mmol) 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles be in the methylene dichloride of 3:1 and the mixing solutions of ethanol, under being heated to 60 DEG C of states, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.58g, yield is 59.2%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z): 979.1 (M ⁺); Its ultimate analysis is: C ₃₅h ₂₁f ₁₃irN ₇, theoretical value: C, 42.95; H, 2.16; F, 25.23; Ir, 19.64; N, 10.02; Measured value: C, 42.86; H, 2.23; F, 25.27; Ir, 19.58; N, 10.06.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium.

Two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 455nm place, has an acromion at 485nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.25

Embodiment 3: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

It adopts following steps to obtain:

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 2.48g (11mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50ml DMF, stir 10min.The aqueous solution of 25ml containing 3.18g (30mmol) sodium carbonate is dripped 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 1/3 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 37.9%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 274.0 (M ⁺); Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₂h ₇f ₅n ₂, theoretical value: C, 52.57; H, 2.57; F, 34.64; N, 10.22; Measured value: C, 52.52; H, 2.64; F, 34.57; N, 10.27.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-5-methylpyrimidine.

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.71g (2mmol) three hydrated iridium trichloride, 1.64g (6mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) to be dissolved in 50ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-methylpyrimidine, is heated to stirring reaction 22h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.90g, yield is 58.1%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the synthesis of iridium

Building-up reactions formula is as follows:

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.64g (0.5mmol) part be 2-(2', 6'-difluoro pyridine-3'-base)-5-methylpyrimidine containing iridium dichloro dimer and 0.27g (1.25mmol) ₃it is in the trichloromethane of 3:1 and the mixing solutions of ethanol that-trifluoromethyl-5-(pyridine-2'-base) pyrazoles is dissolved in 40ml volume ratio, under being heated to reflux state, and stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying pure products 0.40g, yield is 49.0%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 951.1 (M ⁺); Its ultimate analysis is: C ₃₃h ₁₇f ₁₃irN ₇, theoretical value: C, 41.69; H, 1.80; F, 25.98; Ir, 20.22; N, 10.31; Measured value: C, 41.63; H, 1.87; F, 25.92; Ir, 20.28; N, 10.30.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium.

End product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 455nm place, has an acromion at 484nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.13

Embodiment 4: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

it adopts following steps to obtain:

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 2.48g (11mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50ml DMF, stir 10min.The aqueous solution of 25ml containing 3.18g (30mmol) sodium carbonate is dripped 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 1/3 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 37.9%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 274.0 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₂h ₇f ₅n ₂, theoretical value: C, 52.57; H, 2.57; F, 34.64; N, 10.22; Measured value: C, 52.52; H, 2.64; F, 34.57; N, 10.27.

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

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

Reaction formula is as follows:

Concrete steps are: 0.36g (1mmol) three hydrated iridium trichloride, 0.62g (2mmol) ₂it is in the aqueous solution of the cellosolvo of 3:1 that-(2', 6'-difluoro pyridine-3'-base)-5-methylpyrimidine is dissolved in 20ml volume ratio, 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, after drying part be 2-(2', 6'-difluoro pyridine-3'-base)-5-methylpyrimidine containing iridium dichloro dimer 0.32g, yield is 50.0%.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close the synthesis of iridium

Reaction formula is as follows:

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.77g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-5-methylpyrimidine to be dissolved in 40ml volume ratio containing iridium dichloro dimer and 0.34g (1.25mmol) 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles be in the trichloromethane of 3:1 and the mixing solutions of ethanol, under being heated to 80 DEG C of states, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.50g, yield is 49.7%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1007.2 (M ⁺); Its ultimate analysis is: C ₃₇h ₂₅f ₁₃irN ₇, theoretical value: C, 44.14; H, 2.50; F, 24.53; Ir, 19.09; N, 9.74; Measured value: C, 44.11; H, 2.57; F, 24.45; Ir, 19.15; N, 9.72.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methylpyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium.

Electroluminescent organic material is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 454nm place, has an acromion at 484nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.12.

Embodiment 5: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

it adopts following steps to obtain:

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, the bromo-5-t-butyl pyrimidines of 2.15g (10mmol) 2-, 3.39g (15mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 35ml DMF, stir 10min.The aqueous solution of 15ml containing 1.38g (10mmol) salt of wormwood is dripped 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 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.95g, yield is 30.0%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 316.1 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₅h ₁₃f ₅n ₂, theoretical value: C, 56.96; H, 4.14; F, 30.04; N, 8.86; Measured value: C, 56.90; H, 4.22; F, 30.01; N, 8.87.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-5-t-butyl pyrimidines.

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.70g (2.2mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-5-t-butyl pyrimidines is dissolved in 20ml2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.41g, yield is 47.8%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the synthesis of iridium

Reaction formula is as follows:

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.86g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-5-t-butyl pyrimidines be dissolved in that 50ml volume ratio is 3:1 containing iridium dichloro dimer and 0.43g (2mmol) 3-trifluoromethyl-5-(pyridine-2-base) pyrazoles 1, in the mixing solutions of 2-ethylene dichloride and ethanol, under being heated to reflux state, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.45g, yield is 43.5%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1035.2 (M ⁺); Its ultimate analysis is: C ₃₉h ₂₉f ₁₃irN ₇, theoretical value: C, 45.26; H, 2.82; F, 23.87; Ir, 18.57; N, 9.47; Measured value: C, 45.22; H, 2.87; F, 23.84; Ir, 18.65; N, 9.42.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium.

Electroluminescent organic material is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 463nm place, has an acromion at 492nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.30.

Embodiment 6: electroluminescent organic material disclosed in the present embodiment is: title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

It adopts following steps to obtain:

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

Under nitrogen atmosphere, the bromo-5-t-butyl pyrimidines of 2.15g (10mmol) 2-, 3.39g (15mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 35ml DMF, stir 10min.The aqueous solution of 15ml containing 1.38g (10mmol) salt of wormwood is dripped 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 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.95g, yield is 30.0%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 316.1 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₅h ₁₃f ₅n ₂, theoretical value: C, 56.96; H, 4.14; F, 30.04; N, 8.86; Measured value: C, 56.90; H, 4.22; F, 30.01; N, 8.87.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-5-t-butyl pyrimidines.

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

Concrete steps are: under nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.70g (2.2mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-5-t-butyl pyrimidines is dissolved in 20ml2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.41g, yield is 47.8%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close the synthesis of iridium

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.86g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-5-t-butyl pyrimidines be dissolved in that 50ml volume ratio is 3:1 containing iridium dichloro dimer and 0.54g (2mmol) 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles 1, in the mixing solutions of 2-ethylene dichloride and ethanol, under being heated to reflux state, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.43g, yield is 39.4%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1091.2 (M ⁺); Its ultimate analysis is: C ₄₃h ₃₇f ₁₃irN ₇, theoretical value: C, 47.34; H, 3.42; F, 22.64; Ir, 17.62; N, 8.99; Measured value: C, 47.27; H, 3.51; F, 22.59; Ir, 17.66; N, 8.97.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-t-butyl pyrimidines-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium.

Electroluminescent organic material end product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 462nm place, has an acromion at 492nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.28.

Embodiment 7: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-3'-trifluoromethyl of 4', 6'-bis-)-4-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

It adopts following steps to obtain:

(1) synthesis of 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-4-methoxy pyrimidine

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, the bromo-4-methoxy pyrimidine of 1.89g (10mmol) 2-, 2.71g (12mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40ml toluene, continue to stir 10min.The aqueous solution of 20ml containing 2.76g (20mmol) salt of wormwood is dripped 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 1/3 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 35.8%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 290.0 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₂h ₇f ₅n ₂o, theoretical value: C, 49.67; H, 2.43; F, 32.73; N, 9.65; O, 5.51; Measured value: C, 49.63; H, 2.49; F, 32.66; N, 9.74; O, 5.48.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-4-methoxy pyrimidine.

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

Reaction formula is as follows:

Concrete steps are: under nitrogen atmosphere, 0.71g (2mmol) three hydrated iridium trichloride, 1.74g (6mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) to be dissolved in 50ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-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 0.89g after drying, yield is 55.2%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-4-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the synthesis of iridium

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.81g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-4-methoxy pyrimidine to be dissolved in 30ml volume ratio containing iridium dichloro dimer and 0.32g (1.5mmol) 3-trifluoromethyl-5-(pyridine-2-base) pyrazoles be in the trichloromethane of 3:1 and the mixing solutions of ethanol, under being heated to reflux state, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.48g, yield is 48.8%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 983.1 (M ⁺); Its ultimate analysis is: C ₃₃h ₁₇f ₁₃irN ₇o ₂, theoretical value: C, 40.33; H, 1.74; F, 25.13; Ir, 19.56; N, 9.98; O, 3.26; Measured value: C, 40.26; H, 1.83; F, 25.06; Ir, 19.64; N, 9.94; O, 3.27.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium.

Electroluminescent organic material is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 457nm place, has an acromion at 486nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.12.

Embodiment 8: electroluminescent organic material disclosed in the present embodiment is title complex two (2-(the fluoro-3'-trifluoromethyl of 4', 6'-bis-)-4-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium, its structural formula is as follows:

It adopts following steps to obtain:

(1) synthesis of 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-4-methoxy pyrimidine

Concrete steps are: under nitrogen atmosphere, the bromo-4-methoxy pyrimidine of 1.89g (10mmol) 2-, 2.71g (12mmol) 2, the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40ml toluene, continue to stir 10min.The aqueous solution of 20ml containing 2.76g (20mmol) salt of wormwood is dripped 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 1/3 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 35.8%.

Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 290.0 (M ⁺).Carry out ultimate analysis to described solid to obtain: its molecular formula is C ₁₂h ₇f ₅n ₂o, theoretical value: C, 49.67; H, 2.43; F, 32.73; N, 9.65; O, 5.51; Measured value: C, 49.63; H, 2.49; F, 32.66; N, 9.74; O, 5.48.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(the fluoro-3'-trifluoromethyl of 2', 4'-bis-)-4-methoxy pyrimidine.

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

Concrete steps are: under nitrogen atmosphere, 0.71g (2mmol) three hydrated iridium trichloride, 1.74g (6mmol) 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-) to be dissolved in 50ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-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 0.89g after drying, yield is 55.2%.Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-4-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close the synthesis of iridium

Reaction formula is as follows:

The concrete steps of described electroluminescent organic material are: under nitrogen atmosphere, 0.81g (0.5mmol) part is 2-(2', the fluoro-3'-trifluoromethyl of 4'-bis-)-4-methoxy pyrimidine to be dissolved in 30ml volume ratio containing iridium dichloro dimer and 0.40g (1.5mmol) 3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles be in the trichloromethane of 3:1 and the mixing solutions of ethanol, under being heated to reflux state, stirring reaction 24h.Naturally be chilled to room temperature, remove solvent under reduced pressure.Take volume ratio as the methylene dichloride of 9:1 and methyl alcohol mixed liquor for eluent carries out silica gel column chromatography separating-purifying to crude product, after drying final title complex 0.46g, yield is 44.3%.

Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1039.2 (M ⁺); Its ultimate analysis is: C ₃₇h ₂₅f ₁₃irN ₇o ₂, theoretical value: C, 42.78; H, 2.43; F, 23.77; Ir, 18.50; N, 9.44; O, 3.08; Measured value: C, 42.74; H, 2.49; F, 23.73; Ir, 18.55; N, 9.40; O, 3.09.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-)-4-methoxy pyrimidine-N, C ^2') (3-trifluoromethyl-5-(4-tert .-butylpyridine-2-base) pyrazoles) close iridium.

Electroluminescent organic material is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of the emmission spectrum M), at 456nm place, has an acromion at 486nm place, with the Ir of same concentrations (ppy) simultaneously ₃cH ₂cl ₂solution is standard (Φ _pL=0.40) Φ of end product, is recorded _pL=0.11.

Embodiment 9: with the title complex that embodiment 1 is obtained two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close iridium as luminescent layer doping object organic electroluminescence device, structure as shown in Figure 3:

This organic electroluminescence device comprise stack gradually substrate, anode layer 301, hole transmission layer 302, luminescent layer 303, electron transfer layer 304, buffer layer 305 and cathode layer 306.Wherein:

Substrate adopts glass (Glass), and the material of anode layer 301 is that ITO, ITO are prepared in glass surface, is called for short ito glass together with glass.Certainly, the material of anode layer 301 also can be FTO, AZO, IZO.Be preferably the ITO(tin indium oxide that square resistance is 10-20 Ω), thickness is 100nm;

The material of hole injection layer 302 is PEDOT:PSS (poly-3,4-ethylene dioxythiophene polystyrene doped sulfonate), thickness 40nm;

The material of luminescent layer 303 is be two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, C prepared by 12% embodiment 1 doped with massfraction ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the PVK (Polyvinyl carbazole) of iridium, thickness 50nm;

The material of electron transfer layer 304 is TmPyPB (1,3,5-tri-(m-pyridin-3-yl phenyl) benzene) material, and thickness is 20nm;

The material of buffer layer 305 is LiF, thickness 1nm;

The material of cathode layer 306 is Al layer, thickness 120nm.

The structure of this organic electroluminescence device is: ITO (100nm)/PEDOT:PSS (40nm)/PVK:15wt%Ir title complex (50nm)/TmPyPB (20nm)/LiF (1nm)/Al (120nm); Wherein, brace "/" represents laminate structure, P ₁: the colon ": " in FIrpic represents doping.

The preparation technology of this organic electroluminescence device is as follows:

On the glass-based plate of pre-washing and UV-ozone process, a layer thickness is 100nm, square resistance is 10 ~ 20 Ω tin indium oxide (ITO) is deposited as transparent anode 301 at one, on anode 301, the PEDOT:PSS (poly-3 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4-ethylenedioxy thiophene polystyrene doped sulfonate) hole-injecting material as hole injection layer 302, in nitrogen atmosphere, toast 10min at 120 DEG C of temperature; Chlorobenzene solution spin coating a layer thickness is two (2-(the fluoro-5'-trifluoromethyl of 4', 6'-bis-) pyrimidine-N, the C that prepare doped with 12wt% embodiment 2 of 50nm ^2') (3-trifluoromethyl-5-(pyridine-2-base) pyrazoles) close the PVK (Polyvinyl carbazole) of iridium as luminescent layer 303; Then on this luminescent layer 303 spin coating a layer thickness be TmPyPB (1,3,5-tri-(the m-pyridin-3-yl phenyl) benzene) material of 20nm as electron transfer layer 304,80 DEG C of anneal 60min; Last vacuum evaporation a layer thickness be the LiF of 1nm as electron injection buffer layer 305, adopt vacuum plating techniques of deposition thickness to be the metal A l of 120nm on the buffer layer, as the negative electrode 306 of device.

Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested, with French JY company SPEX CCD by Keithley source measuring system (Keithley2400Sourcemeter) ₃its electroluminescent spectrum of 000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, and the maximum emission wavelength recording organic electroluminescence device, at 458nm place, has an acromion at 487nm place, the maximum external quantum efficiency of device is 9.7%, and maximum lumen efficiency is 8.8lm/W.

Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.

Claims (10)

1. there is the electroluminescent organic material of following general formula (P):

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy; R ₂for hydrogen atom or the tertiary butyl.

2. electroluminescent organic material as claimed in claim 1, is characterized in that, described R ₁be positioned 4-or the 5-position of its place pyrimidine.

3. a preparation method for electroluminescent organic material, the method comprises the following steps:

E () provides following compd A and compd B:

Described compd A is described compd B is

F () is under atmosphere of inert gases, adding by volume ratio by described compd A and described compd B according to the mol ratio of 1:2.5 ~ 1:4 is in the mixed solvent that forms of the reaction solvent of 3:1 and ethanol, ligand exchange reaction is carried out under reflux temperature, separating-purifying reaction solution, obtains the electroluminescent organic material of following general formula (P):

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy; R ₂for hydrogen atom or the tertiary butyl.

4. preparation method according to claim 3, is characterized in that, in step (b), described reaction solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.

5. preparation method according to claim 3, is characterized in that, in step (b), the concentration range of described compd A in described mixed solvent is 0.01 ~ 0.0167mol/L.

6. preparation method according to claim 3, is characterized in that, described compd A adopts following steps to obtain:

C () provides following Compound C and Compound D:

Described Compound C is described Compound D is IrCl ₃3H ₂o,

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy;

D () is under atmosphere of inert gases, described Compound C and described Compound D are added in the cellosolvo aqueous solution according to the mol ratio of 2.2:1 ~ 3:1, the volume ratio of cellosolvo and water is 3:1, the concentration range of wherein said Compound D in the described cellosolvo aqueous solution is 0.02 ~ 0.05mol/L, be heated to stirring reaction 22 ~ 25h under reflux state, obtain described compd A.

7. preparation method according to claim 6, is characterized in that, described Compound C adopts following steps to obtain:

A () provides following compd E and compound F 17-hydroxy-corticosterone;

Described compd E is described compound F 17-hydroxy-corticosterone is

Wherein, R ₁for hydrogen atom, C _{1 ~ 20}straight chained alkyl, C _{1 ~ 20}branched-chain alkyl, C _{1 ~ 20}unbranched alkoxy or C _{1 ~ 20}branched alkoxy.

B () is under atmosphere of inert gases, be that described compd E and the described compound F 17-hydroxy-corticosterone of 1:1 ~ 1:1.5 is dissolved in organic solvent by palladium catalyst, mol ratio, then drip alkaline solution and reheat Suzuki linked reaction 6 ~ 12h to 85 ~ 100 DEG C of temperature, after being cooled to room temperature, separating-purifying reaction solution, obtains described Compound C.

8. want the preparation method described in 7 according to right, it is characterized in that, described palladium catalyst closes palladium for two chlorine two (triphenyl phosphorus) or four (triphenyl phosphorus) close palladium, described alkaline solution is solution of potassium carbonate or sodium carbonate solution, described organic solvent is toluene solution or DMF solution.

9. preparation method according to claim 7, is characterized in that, the mol ratio of described palladium catalyst and described compd E is 0.03 ~ 0.05:1; Alkali solute in described alkaline solution and the mol ratio of described compd E are 1 ~ 3:1.

10. an organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that, the material of described luminescent layer is electroluminescent organic material according to claim 1.