CN104140447A - Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device - Google Patents
Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device Download PDFInfo
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- CN104140447A CN104140447A CN201310169129.0A CN201310169129A CN104140447A CN 104140447 A CN104140447 A CN 104140447A CN 201310169129 A CN201310169129 A CN 201310169129A CN 104140447 A CN104140447 A CN 104140447A
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- 0 *c(cc1)ccc1-c1cc(cccc2)c2nn1 Chemical compound *c(cc1)ccc1-c1cc(cccc2)c2nn1 0.000 description 1
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Abstract
The invention provides a red organic electrophosphorescent material iridium metal complex with the structure represented by formula (1). In the formula (1), R is a hydrogen atom or a C1-C4 straight chain or alkoxy group. The red organic electrophosphorescent material iridium metal complex is prepared through the following steps: carrying out a Suzuki coupling reaction on an iridium metal complex to prepare a cyclomedtalating ligand, carrying out a polymerization reaction on the cyclomedtalating ligand and chromium trichloride hexahydrate in a 2-ethoxyethanol and water mixed solvent to obtain a chlorendic dimer, and carrying out a complex reaction on the chlorendic dimer and the cyclomedtalating ligand to obtain the red organic electrophosphorescent material iridium metal complex represented by formula (1). The above material has good energy transmission efficiency and appropriate red light emitting wavelength, and can be widely used to make red or white phosphorescent electroluminescent devices in order to reduce the power consumption of the devices, improve the performances of the devices and prolong the life of the devices.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescence device (OLED) is a kind of taking organic materials as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, luminous, response are fast, reduce power consumption, has application prospect very widely in fields such as demonstration, illuminations.
Electroluminescent organic material can be divided into two kinds of fluorescent material and phosphor materials.In fluorescence electroluminescent device, due to the restriction that is subject to spinning and prohibiting, the excited singlet state that produces fluorescence only accounts for whole 25% of the sum that excites, and makes the luminous efficiency of device not high.And using phosphor material as electroluminescent material, can make singlet state and triplet exciton all be utilized effectively, external quantum efficiency is improved.Conventionally, in organic phosphorescent material, introduce heavy metal atom and strengthen spin orbit coupling effect, improve the transition rate constant of electron spinning upset, thereby improve phosphorescence rate constant and phosphorescence quantum yield, finally improve the luminescent properties of organic electroluminescence device.
At present, metal iridium (III) compound, due to good stability, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, be widely applied.And in order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Generally speaking, the development of blue phosphorescent material always lags behind ruddiness and green glow, and with regard to single, from this index of purity of color, blue phosphorescent material seldom can be accomplished the purity of color of the dark red light of picture and dark green light so far.For produce gratifying white light OLED, select at present or taking the phosphor material of sky blue light as main, as FIrpic, just that this just requires arranged in pairs or groups red phosphorescence material will be connected to saturated red scarlet is passable.So the ruddiness phosphorescent organic electroluminescent material of developing high color purity is still a large focus of OLED research field.
Summary of the invention
For overcoming the problem of above-mentioned prior art, the invention provides a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex and preparation method thereof and organic electroluminescence device.A kind of ruddiness organic electromechanical phosphorescent material iridium metal complex provided by the invention has good energy transmission efficiency and suitable red light-emitting wavelength.Preparation technology of the present invention is easy to control, and is conducive to the suitability for industrialized production of device, and low processing cost, has very wide commercialized development prospect.Organic electroluminescence device prepared by the present invention can be launched high purity ruddiness, and has the excellent performances such as luminous efficiency is high, good stability.
First aspect, the invention provides a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1), taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes, in formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
In above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, taking 3-phenyl cinnolines as cyclic metal complexes agent structure, can obtain and be satisfied with red light-emitting wavelength by the straight or branched alkoxy base of the C1～C4 of different C position introducing on phenyl ring, and produce to a certain extent space steric effect, thereby the direct effect between minimizing atoms metal, the self-quenching phenomenon of minimizing triplet exciton; Simultaneously, the cinnolines group that has larger planar rigidity is conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, thereby improve the electroluminescent properties of device.
Above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex can be widely used in prepares ruddiness or white-light phosphor photoelectricity electroluminescence device.
Second aspect, the invention provides a kind of preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the following steps:
(1) compd A and the compd B that provide respectively following structural formula to represent:
In formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4;
(2), under the condition of catalyzer, alkali, organic solvent and protection of inert gas, by after compd A and compd B 1:1 in molar ratio～1:1.5 mixing, reflux is carried out Suzuki linked reaction 10～18 hours, obtains cyclic metal complexes;
(3) under protection of inert gas, by the cyclic metal complexes obtaining in step (2) and hydration iridous chloride with mol ratio 2:1～4:1 in the mixed solvent of cellosolvo and water, be heated to reflux and carry out polyreaction 20～24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is:
Wherein, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4;
(4) under protection of inert gas; the chlorine bridge dipolymer obtaining in step (3) and described cyclic metal complexes are heated in the second organic solvent with mol ratio 1:2～1:4 reflux and carry out complex reaction 5～12 hours; obtain ruddiness organic electromechanical phosphorescent material iridium metal complex; the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1); taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes; in formula; R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
The reaction formula of described Suzuki linked reaction is as follows:
Wherein, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4.
Wherein, compd A and compd B can directly be bought and obtain or prepare according to existing method from market, and the present invention is not restricted this.Can use respectively B1, B2, B3, B4 for different structure compd B ... represent.
Preferably, the catalyzer that described Suzuki linked reaction adopts is organic palladium catalyzer.More preferably, described catalyzer is that four (triphenyl phosphorus) close palladium (Pd (PPh
3)
4) or two (triphenylphosphine) palladium chloride (II) (Pd (PPh
3)
2cl
2).Preferably, described organic palladium catalyst levels is 2%～6% of compd A mole dosage.
The alkaline solution that described Suzuki linked reaction adopts can be inorganic alkali solution or organic bases solution, inorganic alkali solution can be the aqueous solution of alkali metal hydroxide or alkaline carbonate, can be for example but be not limited to sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, solution of potassium carbonate etc., be preferably sodium carbonate solution, organic bases solution can be tetrabutyl phosphonium bromide aqueous ammonium.
The organic solvent that described Suzuki linked reaction adopts is low-pole or aprotic, polar organic solvent or its mixed solvent, can be for example but be not limited to chloroform, methylene dichloride, glycol dimethyl ether, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), tetrahydrofuran (THF) (THF), toluene, dimethylbenzene or its similar compound, being preferably tetrahydrofuran (THF) (THF); The consumption of organic solvent is enough, so that each reactants dissolved fully reaction.Preferably, the concentration of compd A in reaction system is 0.06～0.13mol/L.
Preferably, after step (2) further comprises the steps: Suzuki linked reaction, cooling reaction solution is to room temperature, in product, add distilled water, extract by ethyl acetate, collect organic phase and be dried, filter, and obtain cyclic metal complexes crude product after steaming solvent.
Preferably, described dry employing anhydrous magnesium sulfate.
Preferably, step (2) further comprises carries out recrystallization purification to cyclic metal complexes crude product employing methyl alcohol, obtains the cyclic metal complexes after purifying.
The reaction formula of the polyreaction in step (3) is as follows:
Wherein, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4.
Preferably; the concrete operations of step (3) are as follows: under protection of inert gas; by cyclic metal complexes and hydration iridous chloride in molar ratio 2:1～4:1 put into reactor; add again the mixed solvent of cellosolvo and water; the concentration that makes hydration iridous chloride is 0.02～0.04mol/L; be heated to reflux state, stirring reaction 20～24 hours, obtains chlorine bridge dipolymer.In mixed solvent, the volume ratio of cellosolvo and water is preferably 3:1.
For fear of light, reaction is produced to induction side reaction, this polyreaction is preferably carried out under lucifuge condition, and actually operating can be for wrapping up transparent glass reactor with aluminium-foil paper.
Preferably, after step (3) further comprises the steps: polyreaction, cooling reaction solution, to room temperature, filters, and gained precipitation adopts absolute ethanol washing 3～5 times, obtains chlorine bridge dipolymer crude product after vacuum-drying.
The chlorine bridge dipolymer obtaining, without through further purifying, can directly drop in next step reaction.
The reaction formula of the complex reaction in step (4) is as follows:
In formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4.
The cyclic metal complexes that step (4) obtains the chlorine bridge dipolymer obtaining in step (3) and step (2) is heated to reflux and carries out complex reaction 5～12 hours in the second organic solvent, generate and all join type complex of iridium, i.e. ruddiness organic electromechanical phosphorescent material iridium metal complex.
Preferably, described the second organic solvent is cellosolvo, 2-methyl cellosolve, methylene dichloride, 1,2-ethylene dichloride or trichloromethane.Preferably, the concentration of chlorine bridge dipolymer in the second organic solvent is 0.005～0.015mol/L.
Preferably, step (4) further comprises the steps: after completion of the reaction, after steaming solvent, the method for employing underpressure distillation obtains iridium metal complex crude product, carry out silica gel column chromatography with methylene dichloride and ethyl acetate mixed solvent again, collect red part, steaming desolventizes, and after being dried, obtains the ruddiness organic electromechanical phosphorescent material iridium metal complex after purifying.
Wherein, in methylene dichloride and ethyl acetate mixed solvent, both ratios can be adjusted according to concrete different iridium metal complex crude products.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, ruddiness organic electromechanical phosphorescent material iridium metal complex has adulterated in described luminescent layer, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1), taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes, in formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
In above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, taking 3-phenyl cinnolines as cyclic metal complexes agent structure, can obtain and be satisfied with red light-emitting wavelength by the straight or branched alkoxy base of the C1～C4 of different C position introducing on phenyl ring, and produce to a certain extent space steric effect, thereby the direct effect between minimizing atoms metal, the self-quenching phenomenon of minimizing triplet exciton; Simultaneously, the cinnolines group that has larger planar rigidity is conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, thereby improve the electroluminescent properties of device.In the preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, adopt better simply synthetic route, technique is easy to control, and is conducive to the suitability for industrialized production of device, greatly reduces the cost of manufacturing, and has very wide commercialized development prospect.In above-mentioned organic electroluminescence device, above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex is doped in the material of main part in organic electroluminescence device luminescent layer as guest materials, can prevent the quenching phenomenon of triplet exciton, and both have good consistency, can be widely used in and prepare ruddiness or white-light phosphor photoelectricity electroluminescence device, reach reduction device power consumption, improve the object of device performance prolongs life.The organic electroluminescence device of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex of having adulterated in luminescent layer can be launched high purity ruddiness, and has good device performance.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural formula of the ruddiness organic electromechanical phosphorescent material iridium metal complex of the embodiment of the present invention;
Fig. 2 is the preparation flow schematic diagram of the ruddiness organic electromechanical phosphorescent material iridium metal complex of the embodiment of the present invention;
Fig. 3 is the utilizing emitted light spectrogram of ruddiness organic electromechanical phosphorescent material iridium metal complex in the embodiment of the present invention 1;
Fig. 4 is the structural representation of organic electroluminescence device in the embodiment of the present invention 5.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1), taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes, in formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
Embodiment 1: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-phenyl cinnolines-N, C
2'] close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
(1) compd A and the compound B-11 that provide respectively following structural formula to represent:
(2) cyclic metal complexes 3-phenyl cinnolines is synthetic
Under nitrogen protection; by 0.83g (4.0mmol) 3-bromine cinnolines; 0.59g (4.8mmol) phenylo boric acid; 0.28g (0.24mmol) tetrakis triphenylphosphine palladium is dissolved in 25mL THF; the wet chemical that is 10% by 10mL massfraction is added dropwise to reaction system, is heated to reflux temperature stirring reaction 18h.After completion of the reaction, question response liquid cooling is to room temperature, the appropriate distilled water of impouring, ethyl acetate extraction.Separatory again, anhydrous magnesium sulfate drying organic phase.Filter, rotation is steamed and is desolventized to obtain crude product.Adopt methyl alcohol to carry out recrystallization again, obtain 0.53g pure products, yield is 64.2%.
Structural Identification:
Mass spectrum (MS m/z): 206.1 (M
+)
Ultimate analysis: C14H10N2
Theoretical value: C, 81.53; H, 4.89; N, 13.58;
Measured value: C, 81.45; H, 4.94; N, 13.61.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-phenyl cinnolines.
(3) main part is the dimeric synthetic containing iridium dichloro of 3-phenyl cinnolines
Under nitrogen protection, by 0.52g (2.5mmol) 3-phenyl cinnolines, it is in the cellosolvo of 3:1 and the mixed solvent of distilled water that 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in 25m volume ratio.Under lucifuge condition, reacting by heating system is to reflux temperature, stirring reaction 24h.After completion of the reaction, be chilled to room temperature, filter, absolute ethanol washing 3 times for gained precipitation, after vacuum-drying winner's part be 3-phenyl cinnolines containing iridium dichloro dimer 0.51g, yield is 79.9%.Crude product, without further purification, can directly drop into next step reaction.
(4) title complex three [3-phenyl cinnolines-N, C
2'] close synthesizing of iridium
Under nitrogen protection, by the main part of 0.32g (0.25mmol) be 3-phenyl cinnolines containing iridium dichloro dimer, 0.21g (1mmol) 2-phenyl cinnolines is dissolved in 25mL2-ethoxy ethanol, is heated to reflux temperature stirring reaction 6h.After completion of the reaction, question response liquid cooling, to room temperature, removes solvent under reduced pressure, obtain crude product, the methylene dichloride that gained crude product is 5:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel, collect red part, steaming desolventizes, and after being dried, obtains 0.15g pure products, and yield is 37.1%.
Structural Identification:
Mass spectrum (MS m/z): 808.2 (M
+)
Ultimate analysis: C42H27IrN6
Theoretical value: C, 62.44; H, 3.37; Ir, 23.79; N, 10.40;
Measured value: C, 62.40; H, 3.39; Ir, 23.85; N, 10.36.
The material that the above-mentioned reaction of above data acknowledgement obtains is three [3-phenyl cinnolines-N, C
2'] close iridium.
As shown in Figure 3, transverse axis is emission wavelength (Wavelength, the nm of unit), and the longitudinal axis is the photoluminescence intensity (Normalized PL Intensity a.u.) after normalization method, and end product title complex is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 625nm place, can be used as ruddiness electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, 10
-5the CH of mol/L end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.38, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-(6'-p-methoxy-phenyl) cinnolines-N, C
2'] close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
(1) compd A and the compd B 2 that provide respectively following structural formula to represent:
(2) cyclic metal complexes 3-(2'-p-methoxy-phenyl) cinnolines is synthetic
Under nitrogen protection; by 0.83g (4.0mmol) 3-bromine cinnolines; 0.61g (4mmol) 2-methoxyphenylboronic acid; 0.23g (0.20mmol) tetrakis triphenylphosphine palladium is dissolved in 25mL toluene; the wet chemical that is 10% by 10mL massfraction is added dropwise to reaction system, is heated to reflux temperature stirring reaction 10h.After completion of the reaction, question response liquid cooling is to room temperature, the appropriate distilled water of impouring, ethyl acetate extraction.Separatory again, anhydrous magnesium sulfate drying organic phase.Filter, rotation is steamed and is desolventized to obtain crude product.Adopt methyl alcohol to carry out recrystallization again, obtain 0.55g pure products, yield is 58.2%.
Structural Identification:
Mass spectrum (MS m/z): 236.1 (M
+)
Ultimate analysis: C15H12N2O
Theoretical value: C, 76.25; H, 5.12; N, 11.86; O, 6.77;
Measured value: C, 76.21; H, 5.18; N, 11.83; O, 6.78.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2'-p-methoxy-phenyl) cinnolines.
(3) main part is the dimeric synthetic containing iridium dichloro of 3-(2'-p-methoxy-phenyl) cinnolines
Under nitrogen protection, by 0.47g (2mmol) 3-(2'-p-methoxy-phenyl) cinnolines, it is in the cellosolvo of 3:1 and the mixed solvent of distilled water that 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in 30mL volume ratio.Under lucifuge condition, reacting by heating system is to reflux temperature stirring reaction 24h.After completion of the reaction, question response liquid cooling is to room temperature, filter, absolute ethanol washing 3 times for gained precipitation, after vacuum-drying winner's part be 3-(2'-p-methoxy-phenyl) cinnolines containing iridium dichloro dimer 0.50g, yield is 71.6%.Crude product, without further purification, can directly drop into next step reaction.
(4) title complex three [3-(6'-p-methoxy-phenyl) cinnolines-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part of 0.35g (0.25mmol) be 3-(2'-p-methoxy-phenyl) cinnolines containing iridium dichloro dimer; 0.18g (0.75mmol) 2-(2'-p-methoxy-phenyl) cinnolines is dissolved in 50mL trichloromethane; heat mixed solution to reflux temperature, stirring reaction 8h.After completion of the reaction, question response liquid cooling, to room temperature, removes solvent under reduced pressure, and the methylene dichloride that residuum is 4:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel, collect red part, and steaming desolventizes, and after being dried, obtains 0.14g pure products, and yield is 31.2%.
Structural Identification:
Mass spectrum (MS m/z): 898.2 (M
+)
Ultimate analysis: C45H33IrN6O3
Theoretical value: C, 60.19; H, 3.70; Ir, 21.41; N, 9.36; O, 5.35;
Measured value: C, 60.13; H, 3.77; Ir, 21.34; N, 9.38; O, 5.38.
The material that the above-mentioned reaction of above data acknowledgement obtains is three [3-(6'-p-methoxy-phenyl) cinnolines-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 630nm place.In addition, 10
-5the CH of mol/L end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.28.
Embodiment 3: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-(5'-ethoxyl phenenyl) cinnolines-N, C
2'] close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
(1) compd A and the compd B 3 that provide respectively following structural formula to represent:
(2) cyclic metal complexes 3-(3'-ethoxyl phenenyl) cinnolines is synthetic
Under nitrogen protection; by 0.83g (4.0mmol) 3-bromine cinnolines; 0.80g (4.8mmol) 2-phenetole boric acid; two (triphenylphosphine) palladiums of 0.28g (0.24mmol) dichloro are dissolved in 30mL DMF; the aqueous sodium carbonate that is 10% by 10mL massfraction is again added dropwise to reaction system, and reacting by heating system is to reflux temperature stirring reaction 12h.After completion of the reaction, question response liquid cooling is to room temperature, and the appropriate distilled water of impouring, adopts and be extracted with ethyl acetate, separatory, anhydrous magnesium sulfate drying organic phase.Filter, rotation is steamed and is desolventized to obtain crude product.Adopt methyl alcohol to carry out recrystallization again, obtain 0.60g pure substance, yield is 59.9%.
Structural Identification:
Mass spectrum (MS m/z): 250.1 (M
+)
Ultimate analysis: C16H14N2O
Theoretical value: C, 76.78; H, 5.64; N, 11.19; O, 6.39;
Measured value: C, 76.73; H, 5.69; N, 11.16; O, 6.42.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(3'-ethoxyl phenenyl) cinnolines.
(3) main part is the dimeric synthetic containing iridium dichloro of 3-(3'-ethoxyl phenenyl) cinnolines
Under nitrogen protection, by 0.62g (2.5mmol) 3-(2'-ethoxyl phenenyl) cinnolines, it is in the cellosolvo of 3:1 and the mixed solvent of distilled water that 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in 30mL volume ratio.Under lucifuge condition, reacting by heating system is to reflux temperature, stirring reaction 20h.After completion of the reaction, question response liquid cooling is filtered to room temperature, absolute ethanol washing 3 times of gained precipitation.After vacuum-drying winner's part be 3-(2'-ethoxyl phenenyl) cinnolines containing iridium dichloro dimer 0.43g, yield is 59.2%.Crude product, without further purification, can directly drop into next step reaction.
(4) title complex three [3-(5'-ethoxyl phenenyl) cinnolines-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part of 0.32g (0.22mmol) be 3-(3'-ethoxyl phenenyl) cinnolines containing iridium dichloro dimer; 0.25g (1mmol) 2-(3'-ethoxyl phenenyl) cinnolines is dissolved in 20mL methylene dichloride, and heating mixed solution is heated to reflux temperature stirring reaction 12h.After completion of the reaction, question response liquid cooling, to room temperature, removes solvent under reduced pressure, the methylene dichloride that residuum is 5:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel.Collect red part, steaming desolventizes, and after being dried, obtains 0.12g pure products, and yield is 29.0%.
Structural Identification:
Mass spectrum (MS m/z): 940.3 (M
+)
Ultimate analysis: C48H39IrN6O3
Theoretical value: C, 61.33; H, 4.18; Ir, 20.45; N, 8.94; O, 5.11;
Measured value: C, 61.36; H, 4.12; Ir, 20.48; N, 8.90; O, 5.14.
The material that the above-mentioned reaction of above data acknowledgement obtains is three [3-(5'-ethoxyl phenenyl) cinnolines-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 622nm place.In addition, 10
-5the CH of mol/L end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.25.
Embodiment 4: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex three [3-(4'-butoxy phenyl) cinnolines-N, C
2'] close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
(1) compd A and the compd B 4 that provide respectively following structural formula to represent:
(2) cyclic metal complexes 3-(4'-butoxy phenyl) cinnolines is synthetic
Under nitrogen protection; by 0.83g (4.0mmol) 3-bromine cinnolines; 1.16g (6mmol) 2-butyl phenyl ether boric acid; two (triphenylphosphine) palladiums of 0.06g (0.08mmol) dichloro are dissolved in 50mL toluene, then the aqueous sodium carbonate that is 10% by 10mL massfraction is added dropwise to reaction system.Reacting by heating system, stirring reaction 15h under reflux temperature.After completion of the reaction, question response liquid cooling is to the appropriate distilled water of impouring after room temperature, after adopting and being extracted with ethyl acetate, and separatory, anhydrous magnesium sulfate drying organic phase.Filter, rotation is steamed and is desolventized to obtain crude product.Adopt methyl alcohol to carry out recrystallization again, obtain 0.50g pure substance, yield is 44.9%.
Structural Identification:
Mass spectrum (MS m/z): 278.1 (M
+)
Ultimate analysis: C18H18N2O
Theoretical value: C, 77.67; H, 6.52; N, 10.06; O, 5.75;
Measured value: C, 77.61; H, 6.59; N, 10.02; O, 5.78.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-butoxy phenyl) cinnolines.
(3) main part is the dimeric synthetic containing iridium dichloro of 3-(4'-butoxy phenyl) cinnolines
Under nitrogen protection, by 1.11g (4mmol) 3-(4'-butoxy phenyl) cinnolines, it is in the cellosolvo of 3:1 and the mixed solvent of distilled water that 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in 50mL volume ratio.Under lucifuge condition, reacting by heating system is to reflux temperature stirring reaction 22h.After question response, cooling reaction solution filters to room temperature, absolute ethanol washing 3 times for gained precipitation, after vacuum-drying corresponding main part be 3-(4'-butoxy phenyl) cinnolines containing iridium dichloro dimer 0.43g, yield is 55.0%.Crude product, without further purification, can directly drop into next step reaction.
(4) title complex three [3-(4'-butoxy phenyl) cinnolines-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part of 0.34g (0.22mmol) be 3-(4'-butoxy phenyl) cinnolines containing iridium dichloro dimer; 0.12g (0.44mmol) 3-(4'-butoxy phenyl) cinnolines is dissolved in 20mL1; in 2-ethylene dichloride, heating mixed solution is to reflux temperature stirring reaction 10h.After completion of the reaction, question response liquid cooling, to room temperature, removes solvent under reduced pressure, and the methylene dichloride that residuum is 5:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel, collect red part, and steaming desolventizes, and after being dried, obtains 0.10g pure products, and yield is 22.2%.
Structural Identification:
Mass spectrum (MS m/z): 1024.4 (M
+)
Ultimate analysis: C54H51IrN6O3
Theoretical value: C, 63.32; H, 5.02; Ir, 18.77; N, 8.21; O, 4.69;
Measured value: C, 63.37; H, 5.00; Ir, 18.72; N, 8.25; O, 4.66.
The material that the above-mentioned reaction of above data acknowledgement obtains is three [3-(4'-butoxy phenyl) cinnolines-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 618nm place.In addition, 10
-5the CH of mol/L end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.22.
Embodiment 5:
The title complex three [3-phenyl cinnolines-N, the C that make with embodiment 1
2'] close the organic electroluminescence device of iridium as luminescent layer doping object, structure as shown in Figure 4:
This device is followed successively by ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt% iridium metal complex (30nm)/BCP (10nm)/Alq
3(20nm)/LiF (2nm)/Al (100nm), on a glass-based plate, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as transparent anode 301, on anode 301, prepare successively by vacuum evaporation the 2-TNATA(4 that a layer thickness is 40nm, 4', 4''-tri-(N-(naphthalene-2-yl)-N-phenyl amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, N '-bis-(1-naphthyl)-N, N '-phenylbenzene benzidine) hole mobile material is as hole transmission layer 303, three [the 3-phenyl cinnolines-N that prepare with a layer thickness embodiment that is 8% doped with massfraction 1 that is 30nm, C
2'] close iridium as luminescent layer 304, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 304 again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) the material Alq3 (three (oxine) aluminium) that is 20nm as hole blocking layer 305, thickness the LiF that is 2nm as electron transfer layer 306, thickness is as electronic injection buffer layer 307, finally on buffer layer, adopt the metal A l that vacuum plating techniques of deposition thickness is 100nm, as the negative electrode 308 of device.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 625nm, and maximum current efficiency is 15.0cd/A, and maximum external quantum efficiency is 7.6%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a ruddiness organic electromechanical phosphorescent material iridium metal complex, it is characterized in that, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1), taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes, in formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
2. a preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, comprises the following steps:
(1) compd A and the compd B that provide respectively following structural formula to represent:
In formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4;
(2), under the condition of catalyzer, alkali, organic solvent and protection of inert gas, by after compd A and compd B 1:1 in molar ratio～1:1.5 mixing, reflux is carried out Suzuki linked reaction 10～18 hours, obtains cyclic metal complexes;
(3) under protection of inert gas, by the cyclic metal complexes obtaining in step (2) and hydration iridous chloride with mol ratio 2:1～4:1 in the mixed solvent of cellosolvo and water, be heated to reflux and carry out polyreaction 20～24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is:
Wherein, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4;
(4) under protection of inert gas; the chlorine bridge dipolymer obtaining in step (3) and described cyclic metal complexes are heated in the second organic solvent with mol ratio 1:2～1:4 reflux and carry out complex reaction 5～12 hours; obtain ruddiness organic electromechanical phosphorescent material iridium metal complex; the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1); taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes; in formula; R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
3. the preparation method of iridium metal complex as claimed in claim 2, is characterized in that, the catalyzer that described Suzuki linked reaction adopts is organic palladium catalyzer; The consumption of described organic palladium catalyzer is 2%～6% of compd A mole dosage.
4. the preparation method of iridium metal complex as claimed in claim 2, is characterized in that, in step (3), the concentration of described hydration iridous chloride in the mixed solvent of cellosolvo and water is 0.02～0.04mol/L.
5. the preparation method of iridium metal complex as claimed in claim 2, is characterized in that, in step (4), described the second organic solvent is cellosolvo, 2-methyl cellosolve, methylene dichloride, 1,2-ethylene dichloride or trichloromethane.
6. the preparation method of iridium metal complex as claimed in claim 2, it is characterized in that, after step (2) further comprises the steps: Suzuki linked reaction, cooling reaction solution is to room temperature, in product, add distilled water, extract by ethyl acetate, collect organic phase and be dried, filter, and obtain cyclic metal complexes crude product after steaming solvent.
7. the preparation method of iridium metal complex as claimed in claim 6, is characterized in that, step (2) further comprises carries out recrystallization purification to described cyclic metal complexes crude product employing methyl alcohol.
8. the preparation method of iridium metal complex as claimed in claim 2, it is characterized in that, after step (3) further comprises the steps: polyreaction, cooling reaction solution is to room temperature, filter, gained precipitation adopts absolute ethanol washing 3～5 times, obtains chlorine bridge dipolymer crude product after vacuum-drying.
9. the preparation method of iridium metal complex as claimed in claim 2, it is characterized in that, step (4) further comprises the steps: after completion of the reaction, after steaming solvent, the method for employing underpressure distillation obtains iridium metal complex crude product, carry out silica gel column chromatography with methylene dichloride and ethyl acetate mixed solvent again, collect red part, steaming desolventizes, and after being dried, obtains the ruddiness organic electromechanical phosphorescent material iridium metal complex after purifying.
10. an organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, it is characterized in that, the described luminescent layer ruddiness organic electromechanical phosphorescent material iridium metal complex that adulterated, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex as the formula (1), taking 3-phenyl cinnolines or derivatives thereof as cyclic metal complexes, in formula, R is the straight or branched alkoxyl group of hydrogen atom or C1～C4
The structural formula of described cyclic metal complexes is:
wherein, n=1～4.
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| US10862055B2 (en) | 2017-05-05 | 2020-12-08 | Universal Display Corporation | Organic electroluminescent materials and devices |
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