CN104418916A - Organic iridium metal complex and preparation method and application thereof - Google Patents

Abstract

The invention discloses an organic iridium metal complex and a preparation method and an application thereof. A molecular structure general formula of the organic iridium metal complex is shown in (I), wherein, R1, R2, R3 in (I) are the same or different H and/or alkyl. The preparation method comprises the steps of preparing a chlorine bridge biopolymer and using the chlorine bridge biopolymer to prepare the organic iridium metal complex with the structure general formula (I). The above organic iridium metal complex takes 2-(3'-cyan-4'-fluorophenyl)pyrimidine as a main structure of an iridium metal ligand, and the organic iridium metal complex has high blue light purity and luminescence efficiency.

Description

Organic iridium metal complex and its preparation method and application

Technical field

The invention belongs to organic electromechanical phosphorescent material technical field, relate to a kind of organic iridium metal complex and its preparation method and application specifically.

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 breakthrough point that the efficiency improving blue light material has just become people to study with purity of color.

So far, constantly deeply, but there is bottleneck problem to the research of organic electromechanical phosphorescent material iridium metal complex in people in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Its major cause be the title complex of existing iridium metals ion on the one hand due to cyclic metal complexes agent structure itself, have impact on the luminescence of phosphor material; On the other hand, easily there is direct effect between the atoms metal in the title complex of metal ion and cause the generation of the self-quenching phenomenon of triplet exciton, thus having had a strong impact on the electroluminescent properties of phosphorescent light-emitting materials.Therefore, the blue phosphorescent organic electroluminescent material how developing high color purity and luminous efficiency becomes the technical barrier expanded blue light material and apply in electroluminescent device.

Summary of the invention

The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of organic iridium metal complex is newly provided, to solve existing organic iridium metal complex blue light color purity and the not high technical problem of luminous efficiency.

Another object of the present invention is to provide a kind of productive rate high, the organic iridium metal complex preparation method be easy to operate and control.

Another object of the present invention is the application providing above-mentioned organic iridium metal complex.

In order to realize foregoing invention object, technical scheme of the present invention is as follows:

A kind of organic iridium metal complex, its general formula of molecular structure is following (I):

In formula, R ₁, R ₂, R ₃identical or not identical is H and/or alkyl.

And a kind of preparation method of organic iridium metal complex, comprises the steps:

The compd A of following structural formula general formula is provided:

In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:

In the environment of anaerobic, by described chlorine bridge dipolymer B and trifluoroacetic acid silver after solvent generation precipitin reaction, removing precipitation and solvent, collecting reaction product;

In the environment of anaerobic, described reaction product and four (1-pyrazoles) the boronation potassium collected is carried out thermal backflow reaction, purifying in reaction solvent, obtains organic iridium metal complex of following general formula of molecular structure (I):

Wherein, the R in compd A, B and general structure (I) ₁, R ₂, R ₃identical or not identical is H and/or alkyl.

And above-mentioned organic iridium metal complex is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.

Above-mentioned organic iridium metal complex is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and change boron for assistant ligand with four (1-pyrazoles), give the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength; When the R substituent group on pyrimidine ring is for alkyl, the electro mass-energy of giving of the alkyl one side alkyl of this introducing obtains satisfied blue light emitting wavelength, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and produce certain space steric effect, thus the direct effect between atoms metal can be stoped, significantly reduce the self-quenching phenomenon of triplet exciton; The introducing that on phenyl ring, strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity assistant ligand four (1-pyrazoles) change boron can also improve luminescent properties, is beneficial to evaporation, increases film-forming properties and improves the stability of device.

Above-mentioned organic iridium metal complex preparation method only needs 2-4 to walk the reaction of ripe type, and target product is easily deducted a percentage, and productive rate is high, and its reaction is easy to operate and control, and is suitable for suitability for industrialized production.

Accompanying drawing explanation

Fig. 1 is the schema of the organic iridium metal complex preparation method of the embodiment of the present invention;

Fig. 2 be embodiment 1 prepare two (2-(4'-cyano group-5'-fluorophenyl) pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the spectroscopic analysis figure of iridium metal complex;

Fig. 3 is two (2-(4'-cyano group-5'-fluorophenyl) pyrimidine-N, the C that prepare with embodiment 1 ^2') (four (1-pyrazoles) change boron) close the OLED structure schematic diagram that iridium metal complex is electroluminescent organic material.

Embodiment

In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.

The invention provides and a kind ofly have blue light color purity and the high organic iridium metal complex of luminous efficiency, its general formula of molecular structure is following (I):

Particularly, the R in (I) formula ₁, R ₂, R ₃identical or not identical is H and/or alkyl.Therefore, this general formula of molecular structure (I) organic iridium metal complex at least has following several molecular structural formula:

Ra, Rb, Rc in above-mentioned I 1 to I 7 molecular structural formula are identical or not identical alkyl.

Lead in organic iridium metal complex of formula I at said structure, on pyrimidine ring, the introducing of alkyl mainly has the effect of following aspect:

1. it has to electronic property, makes the emission wavelength blue shift of this organic iridium metal complex, obtains satisfied blue light emitting wavelength;

2. increase the branch arm of this organic iridium metal complex, thus increase the three-dimensional space steric effect of this organic iridium metal complex, stop the interaction between molecule and accumulation, effectively suppress organic iridium metal complex crystallinity, improve organic iridium metal complex solvability and film forming properties;

3. simultaneously due to alkyl introducing, add the three-dimensional space steric effect of this organic iridium metal complex, effectively reduce the interatomic direct effect of iridium metals, thus significantly reduce the self-quenching phenomenon of triplet exciton.

Therefore, in order to make organic iridium metal complex in above-described embodiment, there is more excellent three-dimensional space steric effect, as the preferred embodiments of the present invention, this organic iridium metal complex is preferably organic iridium metal complex of above-mentioned I 3 to I 7, be more preferably organic iridium metal complex that molecular structural formula is I 7, namely said structure leads to the R in organic iridium metal complex of formula I ₁, R ₂, R ₃be alkyl group.

In further preferred embodiment, the alkyl representated by Ra, Rb, Rc in this above-mentioned I 1 to I 7 molecular structural formula is C ₁~ C ₂₀straight or branched alkyl group.

In a particular embodiment, be also the preferred embodiment of the invention, the alkyl group in the various embodiments described above is methyl (-CH ₃), the tertiary butyl (-C (CH ₃) ₃), in n-hexyl, NSC 62789 base etc. any one, two or three.

Thus, organic iridium metal complex of above-mentioned general formula of molecular structure (I) is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and change boron for assistant ligand with four (1-pyrazoles), give the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength, the concrete organic iridium metal complex utilizing emitted light spectrogram as Examples below 1 preparation; When the R substituent group on pyrimidine ring is for alkyl, the electro mass-energy of giving of the alkyl one side alkyl of this introducing obtains satisfied blue light emitting wavelength, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and produce certain space steric effect, thus the direct effect between atoms metal can be stoped, significantly reduce the self-quenching phenomenon of triplet exciton; In addition, by the selection of rolling into a ball alkyl substituent, the space steric effect of this organic iridium metal complex and solvent borne and film-forming properties can be improved further.Therefore, the introducing that on phenyl ring, strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity 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.

Correspondingly, the embodiment of the present invention additionally provides the method that one may be used for the organic iridium metal complex preparing above-mentioned general formula of molecular structure (I), and its preparation method flow process as shown in Figure 1.This organic iridium metal complex preparation method comprises the steps:

S01., the compd A of following structural formula general formula is provided;

S02. compd A is utilized to prepare chlorine bridge dipolymer B: in the environment of anaerobic, the compd A provided in step S01 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:

S03. chlorine bridge dipolymer B and trifluoroacetic acid silver reacts: in the environment of anaerobic, by the described chlorine bridge dipolymer B for preparing in step S02 with trifluoroacetic acid silver after solvent generation precipitin reaction, remove and precipitate and solvent, collecting reaction product;

S04. the reaction product prepared by step S03 and four (1-pyrazoles) boronation potassium carries out organic iridium metal complex that ligand exchange reaction prepares general formula of molecular structure (I): in the environment of anaerobic, the described reaction product and four of collecting in step S03 (1-pyrazoles) boronation potassium is carried out thermal backflow reaction (i.e. ligand exchange reaction) in reaction solvent, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):

Particularly, in above-mentioned steps S01, the R in compd A molecular structural formula ₁, R ₂, R ₃identical or not identical is H and/or alkyl.Due to the ring master metal ligand structure that compd A is the organic iridium metal complex of above-described embodiment.Therefore, compd A at least has 7 kinds of structural formulas of (I 1) to (I 7) be similar to as organic iridium metal complex of above-mentioned general formula of molecular structure (I), in order to save length, does not repeat them here.

As preferred embodiment, above-claimed cpd A can be prepared as follows:

In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,

Particularly, to carry out the chemical equation of Suzuki linked reaction as follows for this Compound C and 3-cyano group-4-fluorobenzoic boric acid:

Wherein, the R in Compound C ₁, R ₂, R ₃identical or not identical is H and/or alkyl, and it can be directly commercial or be prepared acquisition according to vitochemical ultimate principle.

In this Suzuki linked reaction, the condition of this Suzuki coupled reaction can directly be arranged according to the condition of the Suzuki coupled reaction of existing routine.In order to improve the Suzuki coupled reaction speed between Compound Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the condition setting of this Suzuki coupled reaction is: temperature is 85 ~ 100 DEG C, and the reaction times is 6 ~ 12 hours.

In addition, the consumption of the reactant compound C in this Suzuki linked reaction and 3-cyano group-4-fluorobenzoic boric acid can directly add according to ratio in both chemical equation.In order to impel the Suzuki coupled reaction speed between Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the mol ratio of reactant compound C and 3-cyano group-4-fluorobenzoic boric acid consumption is 1:(1 ~ 1.5).In another preferred embodiment, the concentration of this Compound C in reaction solvent is 0.1 ~ 0.2mol/L.In a particular embodiment, this reaction solvent can select the solvent that Suzuki coupled reaction is conventional, in a preferred embodiment, this reaction solvent is the mixed solvent of volume ratio close to 2:1 of organic solvent and water, wherein, this organic solvent can be dimethyl formamide (DMF), toluene etc.

Organo-metallic palladium catalyst in this Suzuki linked reaction, in further preferred embodiment, this organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium.In another preferred embodiment, the mole dosage of this organo-metallic palladium catalyst and 2 ~ 5% of Compound C mole dosage.

As further preferred embodiment, this organo-metallic palladium catalyst is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium, and 2 ~ 5% of the mole dosage of organo-metallic palladium catalyst and Compound C mole dosage.

Alkaline environment in this Suzuki linked reaction ensure that carrying out smoothly of Suzuki linked reaction, and wherein, alkaline environment can be provided, as Cs by the basic cpd that Suzuki linked reaction is conventional ₂cO ₃, K ₂cO ₃, Na ₂cO ₃in one or more mixture, its addition is 1 ~ 3 times of Compound C mole dosage.

Purification process through Suzuki linked reaction products therefrom can operate according to the method for Examples below 1.

In above-mentioned steps S02, hydrated iridium trichloride can be expressed as IrCl ₃xH ₂o, hydration chlorine sub-iridium acid sodium can be expressed as Na ₃irCl ₆xH ₂o, wherein, x value is preferably 1 ~ 3.Therefore, IrCl ₃xH ₂o can be IrCl ₃3H ₂o, Na ₃irCl ₆xH ₂o can be Na ₃irCl ₆3H ₂o.Certainly, x can also be other values, and like this, hydrated iridium trichloride, hydration chlorine sub-iridium acid sodium also can also be other hydrates.

The temperature of the thermal backflow reaction in this step S02 is determined according to the boiling nature of selected reaction solvent.And this reaction solvent is preferably the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water.Be more preferably the mixture of cellosolvo and distilled water.Therefore, the temperature that in this step S02, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent, and at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 20 ~ 30 hours.Certainly, this reaction solvent also can select other alcohol derivate solvent, can also select other organic solvents, therefore, temperature, the time of this step thermal backflow reaction can also be other temperature, time, and when temperature is relatively low, the thermal backflow time can correspondingly extend.

Oxygen-free environment in this step S02 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of chlorine bridge dipolymer B.

The chemical equation that compd A in this step S02 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium react through thermal backflow is as follows:

Therefore, in above-mentioned steps S02, compd A is 2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium theory, therefore, in order to allow hydrated iridium trichloride or the abundant complete reaction of the sub-iridium acid sodium of hydration chlorine, then compd A is preferably >=2:1 with the mole dosage ratio of iridous chloride or hydration chlorine sub-iridium acid sodium, is preferably (2 ~ 4): 1.Wherein, the concentration range of this iridic compound in reaction solvent is preferably 0.1 ~ 0.2mmol/L.Certainly, compd A also can be allowed fully to react, therefore, compd A is preferably≤2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium.

After the thermal backflow cyclization of step S02, reacted product carried out filter, after purifying and drying treatment, obtain pure compd B.The method of this purifying can be undertaken by the purification process of Examples below 1.

Because the compd B of preparation contains compd A cyclic metal complexes agent structure, again because compd A at least exists 7 kinds of structural formulas mentioned above, therefore compd B equally at least has the 7 kinds of structural formulas be similar to as this compd A, in order to save length, does not repeat them here.

In above-mentioned steps S03, chlorine bridge dipolymer B dissolve after and trifluoroacetic acid silver-colored between precipitation specific as follows: chlorine bridge dipolymer B is dissolved in organic solvent, form the organic solution of chlorine bridge dipolymer B, then drip the organic solution of trifluoroacetic acid silver wherein, its Ag ion generates AgCl with the Cl ionic reaction in chlorine bridge dipolymer B and precipitates, abundant react after, by the precipitation removing generated, collect filtrate, then by the solvent removing in filtrate, collect reactant.The setting of this step S03, removed by the Cl ion in Ag ion and chlorine bridge dipolymer B, be conducive to the carrying out of ligand exchange reaction in following step S04, namely be to be conducive in step S03 last reaction product of collecting can and four (1-pyrazoles) boronation potassium between forward reaction, thus improve the yield of organic iridium metal complex of general formula of molecular structure (I).

Wherein, chlorine bridge dipolymer B and trifluoroacetic acid silver react and can carry out at room temperature.In order to speed of reaction in this step S03, improve the yield of reaction product, and reduce the consumption of reactant, in a preferred embodiment, trifluoroacetic acid silver is (2 ~ 3) with the mole dosage ratio of chlorine bridge dipolymer B: 1.In addition, the concentration of compd B in reaction solvent is preferably 0.01 ~ 0.025mol/L.

Oxygen-free environment in this step S03 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of reaction product.

In above-mentioned steps S04, the temperature that reaction product product and four (1-pyrazoles) the boronation potassium thermal backflow that step S03 collects is reacted is determined according to the boiling nature of selected reaction solvent.And this reaction solvent is preferably acetonitrile.Therefore, the temperature that in this step S04, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent, and as in a particular embodiment, when acetonitrile selected by back flow reaction solvent, the temperature of this thermal backflow reaction can be set to 81 DEG C.The time of thermal backflow reaction is relevant with the temperature of thermal response, and in order to make reactant fully react, time as relatively low in temperature, the thermal backflow time can correspondingly extend.In a preferred embodiment, at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 20 ~ 30 hours.In a particular embodiment, when acetonitrile selected by back flow reaction solvent, the temperature of this thermal backflow reaction is set to 81 DEG C, and the thermal backflow time is 24 hours.

Oxygen-free environment in this step S04 can carry out, as being vacuum or being full of rare gas element to realize with reference to the mode of above-mentioned steps S03 construction oxygen-free environment.This oxygen-free environment ensure that the stable of reactant, improves the yield of organic iridium metal complex of general formula of molecular structure (I).

The chemical equation of above-mentioned steps S03, S04 two step is as follows:

Therefore, in above-mentioned steps S04, the mole dosage of four (1-pyrazoles) boronation potassium theory and the mole dosage of compd B in step S03 are than being 2:1.In order to make compd B and trifluoroacetic acid silver reaction product abundant complete reaction, four (1-pyrazoles) boronation potassium the mole dosage of mole dosage and compd B in step S03 than being preferably >=2:1, be preferably 1:(2 ~ 3).Wherein, compd B and the concentration of trifluoroacetic acid silver reaction product in reaction solvent are preferably 0.01 ~ 0.025mol/L.

After the thermal backflow cyclization of step S04, reacted product carried out filter, after purifying and drying treatment, obtain organic iridium metal complex of pure general formula of molecular structure (I).The method of this purifying can be carried out according to the purification process of Examples below 1.

Reactant only need be carried out thermal backflow and react by above-mentioned organic iridium metal complex preparation method, and the one-tenth ripening reaction only needing 2-3 to walk is without the need to special equipment and environmental requirement, and its preparation method technique is simple, productive rate is high, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.

Have as above-mentioned high blue light color purity and luminous efficiency just because of the organic iridium metal complex of above-described embodiment, and by the group in cyclic metal complexes agent structure if alkyl group is to the adjustment of emission wavelength, its solubleness, good film-forming property, self-quenching phenomenon incidence is low, there is charge transport properties simultaneously good, therefore, this organic iridium metal complex can as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.In application process, can using organic for embodiment of the present invention iridium metal complex as luminescent layer or with other luminescent material compound uses, prepare and there is stable luminescence, and the electroluminescent device that luminous efficiency is high.

Particularly, when the organic iridium metal complex of above-described embodiment as blue electrophosphorescence at organic electroluminescence device (organic electroluminescent LED, during application OLED), this organic electroluminescence device comprises substrate layer, the first electrode layer, organic function layer and the second electrode lay.Wherein, organic function layer comprises the hole transmission layer of stacked setting, at least one luminescent layer and electron transfer layer, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.

Certainly, the organic function layer of this organic electroluminescence device can also comprise the functional layers such as hole injection layer, electron injecting layer, hole blocking layer, electronic barrier layer, and this functional layer is conveniently stacked to be arranged.Containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this organic electroluminescence device, the material selection material known in this field of other each Rotating fields, its preparation method also can according to the existing method preparation in this area.

Particularly, when the organic iridium metal complex of above-described embodiment is as the application of blue electrophosphorescence material in electrochemical cell luminescent device, this electrochemical cell luminescent device comprises anode, negative electrode and is arranged at least one luminescent layer between this anode, negative electrode, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.Wherein, containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this electrochemical cell luminescent device, the material selection material known in this field of anode, negative electrode, its preparation method also can according to the existing method preparation in this area.

Now in conjunction with the embodiments, the present invention is further elaborated.

Embodiment 1

Two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close iridium metal complex and synthetic method thereof:

(1) the synthesis synthesis of 2-(3'-cyano group-4'-fluorophenyl) pyrimidine:

Under nitrogen protection, 1.59g (10mmol) 2-bromo pyrimi piperidine, 1.98g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system; Heating, stirring reaction 6h under 100 DEG C of state of temperatures.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 1.31g, yield is 65.8%; Its chemical equation is as follows:

2-(3'-cyano group-4'-fluorophenyl) pyrimidine product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 199.0 (M ⁺); Ultimate analysis: C11H6FN3; Theoretical value: C, 66.33; H, 3.04; F, 9.54; N, 21.10; Measured value: C, 66.37; H, 3.02; F, 9.50; N, 21.11.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl) pyrimidine.

(2) part be 2-(3'-cyano group-4'-fluorophenyl) pyrimidine containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.50g (2.5mmol) 2-(3'-cyano group-4'-fluorophenyl) pyrimidine 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, and obtain solids 0.39g after drying, yield is 62.5%; Its chemical equation is as follows:

(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the synthesis of iridium metal complex:

Under nitrogen protection, 0.62g (0.5mmol) main part is that the iridium dichloro dimer that contains of 2-(3'-cyano group-4'-fluorophenyl) pyrimidine is dissolved in 25mL methylene dichloride, 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 0.23g, and productive rate is 26.5%; Its chemical equation is as follows:

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 868.2 (M ⁺); Ultimate analysis: C34H22BF2IrN14; Theoretical value: C, 47.07; H, 2.56; B, 1.25; F, 4.38; Ir, 22.15; N, 22.60; Measured value: C, 47.11; H, 2.50; B, 1.29; F, 4.34; Ir, 22.18; N, 22.58.The material that the above-mentioned reaction of this data acknowledgement obtains is that two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex.

Embodiment 2

Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex and synthetic method thereof:

(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine:

Under nitrogen protection, the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate subsequently in reaction system; Be heated to stirring reaction 8h under 90 DEG C of state of temperatures; 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 1.17g, yield is 54.9%; Its chemical equation is as follows:

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 213.1 (M ⁺); Ultimate analysis: C12H8FN3; Theoretical value: C, 67.60; H, 3.78; F, 8.91; N, 19.71; Measured value: C, 67.66; H, 3.74; F, 8.88; N, 19.72.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine.

(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.43g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-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, and obtain solids 0.36g after drying, yield is 55.2%; Its chemical equation is as follows:

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

Under nitrogen protection, 0.65g (0.5mmol) main part is that the iridium dichloro dimer that contains of 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine is dissolved in 20mL trichloromethane, 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 0.19g, and productive rate is 21.2%; Its chemical equation is as follows:

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 896.2 (M ⁺); Ultimate analysis: C36H26BF2IrN14; Theoretical value: C, 48.27; H, 2.93; B, 1.21; F, 4.24; Ir, 21.46; N, 21.89; Measured value: C, 48.32; H, 2.90; B, 1.25; F, 4.21; Ir, 21.42; N, 21.90.The material that the above-mentioned reaction of above data acknowledgement obtains is that two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex.

Embodiment 3

Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-t-butyl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex and synthetic method thereof:

(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines:

Under nitrogen protection; 2.15g (10mmol) 2-bromo-5-t-butyl pyrimidines, 2.22g (14mmol) 3-cyano group-4-fluorobenzoic boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 1.06g (10mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states; 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 1.17g, yield is 45.8%;

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 255.1 (M ⁺); Ultimate analysis: C15H14FN3; Theoretical value: C, 70.57; H, 5.53; F, 7.44; N, 16.46; Measured value: C, 70.53; H, 5.58; F, 7.42; N, 16.47.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines.

(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, three hydrated iridium trichloride of 1mmol and 0.76g (3mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines are dissolved in 20mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.29g after drying, yield is 39.4%;

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

Under nitrogen protection; 0.59g (0.4mmol) main part is that the iridium dichloro dimer that contains of 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines is dissolved in 25mL methylene dichloride; 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 0.12g, and productive rate is 15.3%;

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 980.3 (M ⁺); Ultimate analysis: C42H38BF2IrN14; Theoretical value: C, 51.48; H, 3.91; B, 1.10; F, 3.88; Ir, 19.62; N, 20.01; Measured value: C, 51.45; H, 3.96; B, 1.06; F, 3.93; Ir, 19.60; N, 20.00.The material that the above-mentioned reaction of above data acknowledgement obtains is that two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-t-butyl pyrimidines-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex.

Embodiment 4

Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close iridium metal complex and synthetic method thereof:

(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine:

Under nitrogen protection, 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.19g (7.5mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system; Be heated to stirring reaction 12h under 85 DEG C of state of temperatures; 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 0.72g, yield is 30.0%;

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 479.4 (M ⁺); Ultimate analysis: C31H46FN3; Theoretical value: C, 77.62; H, 9.67; F, 3.96; N, 8.76; Measured value: C, 77.67; H, 9.61; F, 3.97; N, 8.75.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine.

(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, 0.18g (0.5mmol) three hydrated iridium trichloride, 0.96g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine is dissolved in 10mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.11g after drying, yield is 20.5%; Dipolymer, without the need to further purification, can directly drop in next step reaction.

(3) title complex two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the synthesis of iridium metal complex:

Under nitrogen protection, 0.43g (0.2mmol) main part is that the iridium dichloro dimer that contains of 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine is dissolved in 15mL trichloromethane, 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 0.06g, and productive rate is 10.5%;

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 1428.8 (M ⁺); Ultimate analysis: C74H102BF2IrN14; Theoretical value: C, 62.21; H, 7.20; B, 0.76; F, 2.66; Ir, 13.45; N, 13.73; Measured value: C, 62.26; H, 7.22; B, 0.72; F, 2.63; Ir, 13.42; N, 13.75.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the synthesis of iridium metal complex.

Embodiment 5

Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close iridium metal complex and synthetic method thereof:

(1) the synthesis synthesis of 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidines:

Under nitrogen protection, 1.87g (10mmol) 2-bromine 4,5-dimethyl pyrimidine, 1.98g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system; Heating, stirring reaction 6h under 100 DEG C of state of temperatures.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 1.09g, yield is 48.0%; Its chemical equation is as follows:

2-(3'-cyano group-4'-fluorophenyl) pyrimidine product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 227.1 (M ⁺); Ultimate analysis: C13H10FN3; Theoretical value: C, 68.71; H, 4.44; F, 8.36; N, 18.49; Measured value: C, 68.75; H, 4.37; F, 8.42; N, 18.46.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidines.

(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidines containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, 0.57g (2.5mmol) 2-(3'-cyano group-4'-fluorophenyl)-4, it is in the cellosolvo/water mixed liquid of 3:1 that 5-dimethyl pyrimidine 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, and obtain solids 0.37g after drying, yield is 54.4%; Its chemical equation is as follows:

(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the synthesis of iridium metal complex:

Under nitrogen protection, 0.68g (0.5mmol) part is 2-(3'-cyano group-4'-fluorophenyl)-4, the iridium dichloro dimer that contains of 5-dimethyl pyrimidine is dissolved in 25mL methylene dichloride, 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 0.18g, and productive rate is 19.5%; Its chemical equation is as follows:

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 924.2 (M ⁺); Ultimate analysis: C38H30BF2IrN14; Theoretical value: C, 49.41; H, 3.27; B, 1.17; F, 4.11; Ir, 20.81; N, 21.23; Measured value: C, 49.43; H, 3.22; B, 1.22; F, 4.10; Ir, 20.83; N, 21.20.The material that the above-mentioned reaction of this data acknowledgement obtains is that two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex.

Embodiment 6

Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close iridium metal complex and synthetic method thereof:

(1) the synthesis synthesis of 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine:

Under nitrogen protection, 2.01g (10mmol) 2-bromo-4,5,6-trimethylpyrimidine, 1.98g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system; Heating, stirring reaction 6h under 100 DEG C of state of temperatures.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 0.96g, yield is 39.8%; Its chemical equation is as follows:

2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine products are carried out the result of Structural Identification:

Mass spectrum (MSm/z): 241.0 (M ⁺); Ultimate analysis: C14H12FN3; Theoretical value: C, 69.70; H, 5.01; F, 7.87; N, 17.42; Measured value: C, 69.74; H, 5.03; F, 7.77; N, 17.46.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine.

(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine containing the dimeric synthesis of iridium dichloro:

Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, 0.60g (2.5mmol) 2-(3'-cyano group-4'-fluorophenyl)-4,5, it is in the cellosolvo/water mixed liquid of 3:1 that 6-trimethylpyrimidine 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, and obtain solids 0.26g after drying, yield is 36.7%; Its chemical equation is as follows:

(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C ^2') (four (1-pyrazoles) change boron) close the synthesis of iridium metal complex:

Under nitrogen protection, 0.71g (0.5mmol) part is 2-(3'-cyano group-4'-fluorophenyl)-4,5, the iridium dichloro dimer that contains of 6-trimethylpyrimidine is dissolved in 25mL methylene dichloride, 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 0.12g, and productive rate is 12.6%; Its chemical equation is as follows:

Product is carried out the result of Structural Identification:

Mass spectrum (MS m/z): 952.3 (M ⁺); Ultimate analysis: C40H34BF2IrN14; Theoretical value: C, 50.47; H, 3.60; B, 1.14; F, 3.99; Ir, 20.19; N, 20.60; Measured value: C, 50.43; H, 3.66; B, 1.11; F, 3.96; Ir, 20.25; N, 20.59.The material that the above-mentioned reaction of this data acknowledgement obtains is that two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C2') (four (1-pyrazoles) change boron) closes iridium metal complex.

Comparison example 1

Direct acquisition organic electromechanical phosphorescent material two [2-(4', 6'-difluorophenyl) pyridine-N, C ^2'] (2-pyridinecarboxylic) close iridium (FIrpic), plays structure as follows:

Performance test:

Existing organic iridium metal complex FIrpic in organic iridium metal complex of above-described embodiment 1 ~ 6 preparation and comparison example 1 is carried out spectroscopic analysis and luminous quantum efficiency mensuration, testing method is as follows:

Spectroscopic analysis: the organic iridium metal complex prepared by above-described embodiment 1 ~ 6 respectively compound concentration is 10 ^-6the CH of M ₂c _l2solution, then carries out emmission spectrometric analysis respectively at 298K temperature.

Luminous quantum efficiency measure: by above-described embodiment 1 ~ 6 prepare organic iridium metal complex and comparison example 1 in existing organic iridium metal complex FIrpic respectively compound concentration be 10 ^-6the CH of M ₂c _l2solution, then carries out luminous quantum efficiency mensuration.

The result that emmission spectrometric analysis and luminous quantum efficiency record is as following table 1:

Table 1

Wherein, organic iridium metal complex prepared by above-described embodiment 1 ~ 6 is carrying out in emmission spectrometric analysis respectively, organic iridium metal complex in embodiment 1 has an acromion at 483nm place simultaneously, organic iridium metal complex in embodiment 2 has an acromion at 479nm place simultaneously, organic iridium metal complex in embodiment 3 has an acromion at 488nm place simultaneously, organic iridium metal complex in embodiment 4 has an acromion at 502nm place simultaneously, organic iridium metal complex in embodiment 5 has an acromion at 488nm place simultaneously, organic iridium metal complex in embodiment 6 has an acromion at 489nm place simultaneously.In addition, as shown in Figure 2, in Fig. 2, transverse axis is emission wavelength (unit nm) to the emmission spectrum of organic iridium metal complex prepared by embodiment 1, and the longitudinal axis is the photoluminescence intensity (a.u.) after normalization method.

Can be found out by table 1 and Fig. 2, organic iridium metal complex that the organic iridium metal complex of the embodiment of the present invention is prepared as above-described embodiment 1 ~ 6 is compared with existing organic iridium metal complex, its blue light purity of launching is high, there is higher luminous quantum efficiency, its luminous efficiency is high, therefore, can be used as blue light electroluminescent material to be widely used in technical field of organic electroluminescence.

Application Example 1

Containing organic iridium metal complex organic electroluminescence device (OLED) prepared by embodiment 1 and preparation method thereof:

As shown in Figure 3, it comprises the glass substrate 1, anode layer 2, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 and the cathode layer 4 that stack gradually combination to the structure of this OLED.Wherein, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 form organic function layer 3, two (2-(4'-cyano group-5'-fluorophenyl) pyrimidine-N, C prepared by the embodiment 1 containing 7wt% in this luminescent layer 34 ^2') (four (1-pyrazoles) change boron) close iridium metal complex.Its concrete structure the following is Ir title complex (30nm)/BCP (10nm)/Alq3 (35nm)/LiF (1nm)/Al (120nm) prepared by glass/ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt% embodiment 1.

This OLED preparation method is as follows: a glass substrate 1 depositing a layer thickness is 200nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 2, on anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 31, 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 32, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is two (2-(4'-cyano group-5'-fluorophenyl) pyrimidine-N prepared doped with 7wt% embodiment 1 of 30nm as electronic barrier layer 33 and a layer thickness, C ^2') (four (1-pyrazoles) change boron) close the mCP of iridium as luminescent layer 34, on this luminescent layer 34, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) material be the Alq3 (three (oxine) aluminium) of 35nm as hole blocking layer 35, thickness is that the LiF of 1nm is as electron injection buffer layer 37 as electron transfer layer 36, thickness, 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 4 of device.

Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 463nm, has an acromion at 487nm place.The maximum current efficiency of device is 18.9cd/A, and maximum external quantum efficiency is 10.5%.

The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. an organic iridium metal complex, its general formula of molecular structure is following (I):

In formula, R ₁, R ₂, R ₃identical or not identical is H and/or alkyl.

2. organic iridium metal complex according to claim 1, is characterized in that: described alkyl is C ₁~ C ₂₀straight or branched alkyl.

3. organic iridium metal complex according to claim 1 and 2, is characterized in that: described alkyl be in methyl, the tertiary butyl, n-hexyl, NSC 62789 base any one, two or three.

4. a preparation method for organic iridium metal complex, comprises the steps:

The compd A of following structural formula general formula is provided:

In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:

In the environment of anaerobic, by described chlorine bridge dipolymer B and trifluoroacetic acid silver after solvent generation precipitin reaction, removing precipitation and solvent, collecting reaction product;

In the environment of anaerobic, described reaction product and four (1-pyrazoles) the boronation potassium collected is carried out thermal backflow reaction, purifying in reaction solvent, obtains organic iridium metal complex of following general formula of molecular structure (I):

Wherein, the R in compd A, B and general structure (I) ₁, R ₂, R ₃identical or not identical is H and/or alkyl.

5. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in the step that compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium reacts, the mole dosage of described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium is than being (2 ~ 4): 1.

6. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in the step of described chlorine bridge dipolymer B and the precipitin reaction of trifluoroacetic acid silver, the mole dosage of described trifluoroacetic acid silver and chlorine bridge dipolymer B is than for being (2 ~ 3): 1.

7. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, it is characterized in that: in the step that the thermal backflow of described reaction product and four (1-pyrazoles) boronation potassium is reacted, described four (1-pyrazoles) boronation potassium is (2 ~ 3) with the mole dosage ratio of described compd B: 1.

8. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, it is characterized in that: in the step that described compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium react, described reaction solvent is the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water; And/or,

In the step that the thermal backflow of described reaction product and four (1-pyrazoles) boronation potassium is reacted, described reaction solvent is acetonitrile.

9. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, is characterized in that, the preparation method of described compd A is as follows:

In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,

Wherein, the R in Compound C ₁, R ₂, R ₃identical or not identical is H and/or alkyl.

10. the organic iridium metal complex as described in as arbitrary in claims 1 to 3 is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.