CN104140441A - 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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- CN104140441A CN104140441A CN201310169081.3A CN201310169081A CN104140441A CN 104140441 A CN104140441 A CN 104140441A CN 201310169081 A CN201310169081 A CN 201310169081A CN 104140441 A CN104140441 A CN 104140441A
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- 0 *c1nc(-c2ccccc2)c(-c2ccccc2)c2c1cccc2 Chemical compound *c1nc(-c2ccccc2)c(-c2ccccc2)c2c1cccc2 0.000 description 5
- MAOBFOXLCJIFLV-UHFFFAOYSA-N Nc(cccc1)c1C(c1ccccc1)=O Chemical compound Nc(cccc1)c1C(c1ccccc1)=O MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- UNBZZWNNRZOSSI-UHFFFAOYSA-N Nc1c(C(Cc2ccccc2)(C2N3C2CC3)c2ccccc2)cccc1 Chemical compound Nc1c(C(Cc2ccccc2)(C2N3C2CC3)c2ccccc2)cccc1 UNBZZWNNRZOSSI-UHFFFAOYSA-N 0.000 description 1
- FHRNCCJFBNKRED-UHFFFAOYSA-N c(cc1)ccc1-c1c(-c2ccccc2)nnc2c1cccc2 Chemical compound c(cc1)ccc1-c1c(-c2ccccc2)nnc2c1cccc2 FHRNCCJFBNKRED-UHFFFAOYSA-N 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 Grignard reaction on an iridium metal complex to prepare a compound C, carrying out dehydration cyclization on the compound C to obtain 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 acetylacetone 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 ofly to take 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, in fields such as demonstration, illuminations, has application prospect very widely.
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, in building-up process, reaction conditions is gentle, and has very high electroluminescent properties, is 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 take 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), with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, also comprises assistant ligand, and described assistant ligand is methyl ethyl diketone, in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
In above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, with 3,4-phenylbenzene cinnolines is cyclic metal complexes agent structure, take methyl ethyl diketone as assistant ligand, by the different C position alkoxy base of introducing on the phenyl ring at 3-phenyl, can obtain and be satisfied with red light-emitting wavelength, and produce to a certain extent space steric effect, thus reduce the direct effect between atoms metal, reduce the self-quenching phenomenon of triplet exciton; Simultaneously, the cinnolines group and the 4-phenyl group that have larger planar rigidity are 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 Grignard reagent B that provide following structural formula to represent:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(2) under protection of inert gas, compd A is dissolved in organic solvent, then drips wherein the anhydrous ether solution of Grignard reagent B; after dropwising; reflux 40～45 minutes, then add methyl alcohol and ammonium nitrate quencher reaction, after separation and purification, obtain the Compound C that following structural formula represents:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(3) in the sulfuric acid that is 20% by described Compound C in volume fraction, 100 ℃ are heated 40～50 minutes, add again ammoniacal liquor to regulate pH to 8～9, extracted with diethyl ether obtains one-level product after steaming and desolventizing, gained one-level product is dissolved in acetic acid and concentrated hydrochloric acid mixing solutions, add again sodium nitrite in aqueous solution, after 30～35 minutes, add ammoniacal liquor to regulate pH to 8～9, after separation and purification, obtain cyclic metal complexes;
(4) under protection of inert gas, by the cyclic metal complexes obtaining in step (3) and hydration iridous chloride with mol ratio 2～3:1 in the mixed solvent of cellosolvo and water, be heated to 90 ℃ and carry out polyreaction 20～24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is:
Wherein, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(5) under protection of inert gas and alkali condition; the chlorine bridge dipolymer obtaining in step (4) and methyl ethyl diketone are heated to reflux in the second organic solvent 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); with 3; 4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes; also comprise assistant ligand; described assistant ligand is methyl ethyl diketone; in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
The reaction of described step (2) is grignard reaction, and reaction formula is as follows:
Wherein, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group.
Described in step (2), organic solvent is anhydrous diethyl ether.The anhydrous ether solution of described Grignard reagent B is prepared by following manner: by magnesium grain, benzyl chlorine in molar ratio 1:1～1.1:1 join the anhydrous ether solution that obtains Grignard reagent B in anhydrous diethyl ether.
The add-on of described methyl alcohol and ammonium nitrate is excessive, causes grignard reaction quencher.
Preferably, the described purification procedures of step (2) comprising: after completion of the reaction, cooling reaction solution is to room temperature, and product adopts distilled water to wash, dry, and obtains Compound C crude product after steaming solvent.
Preferably, the described purification procedures of step (2) further comprises carries out recrystallization purification to Compound C crude product employing methyl alcohol, obtains the Compound C after purifying.
In the sulfuric acid that step (3) is 20% by step (2) gained Compound C in volume fraction, 100 ℃ of heating are dehydrated into alkene reaction for 40～45 minutes, add again ammoniacal liquor to regulate pH to 8～9, extracted with diethyl ether obtains one-level product after steaming and desolventizing, gained one-level product is dissolved in acetic acid and concentrated hydrochloric acid, add again sodium nitrite in aqueous solution, after 30～35 minutes, complete diazonium ring closure reaction, after completion of the reaction, add ammoniacal liquor to regulate pH to 8～9, after separation and purification, obtain cyclic metal complexes 3,4-phenylbenzene cinnolines or derivatives thereof.The reaction formula of the reaction of step (3) is as follows:
Wherein, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group.
Preferably, institute's purification procedures of step (3) comprising: first adopt chloroform extraction, then adopt recrystallizing methanol, obtain the cyclic metal complexes after purifying.
Step (4) is polymerization reaction take place under heating condition by the cyclic metal complexes of step (3) gained and hydration iridous chloride, obtains chlorine bridge dipolymer.The reaction formula of polyreaction is as follows:
Wherein, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group.
In mixed solvent, the volume ratio of cellosolvo and water is preferably 3:1.
Preferably, the concentration of hydration iridous chloride in the mixed solvent of cellosolvo and water is 0.014～0.028mol/L.
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 (4) 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.
Resulting chlorine bridge dipolymer, without through further purifying, can directly drop in next step reaction.
The reaction formula of the complex reaction in step (5) is as follows:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group.
Step (5) is heated to resulting chlorine bridge dipolymer and methyl ethyl diketone in step (4) reflux and carries out complex reaction 5～12 hours in the second organic solvent, generates the different type complex of iridium of joining, i.e. ruddiness organic electromechanical phosphorescent material iridium metal complex.
Methyl ethyl diketone adds by stoichiometric ratio is excessive.
Preferably, the mol ratio of chlorine bridge dipolymer and methyl ethyl diketone is 1:3～1:4.
Preferably, 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 0.005～0.017mol/L.
Preferably, step (5) further comprises the steps: after completion of the reaction, after steaming solvent, the method for employing underpressure distillation obtains iridium metal complex crude product, the normal hexane that is 6～12:1 by volume ratio again and ethyl acetate mixed solvent carry out silica gel column chromatography, collect red part, steaming desolventizes, and after being dried, obtains the ruddiness organic electromechanical phosphorescent material iridium metal complex after purifying.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, the ruddiness organic electromechanical phosphorescent material iridium metal complex that adulterated in described luminescent layer, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex is as the formula (1), with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, also comprises assistant ligand, and described assistant ligand is methyl ethyl diketone, in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group base,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
In above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, take methyl ethyl diketone as assistant ligand, by the different C position alkoxy base of introducing on the phenyl ring at 3-phenyl, can obtain and be satisfied with red light-emitting wavelength, and produce to a certain extent space steric effect, thus reduce the direct effect between atoms metal, reduce the self-quenching phenomenon of triplet exciton; Simultaneously, the cinnolines group and the 4-phenyl group that have larger planar rigidity are 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.
Accompanying drawing explanation
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), with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, also comprise assistant ligand, described assistant ligand is methyl ethyl diketone, and in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
Embodiment 1: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex two [3,4-phenylbenzene cinnolines-N, C
2'] (methyl ethyl diketone) 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 Grignard reagent B1 that provide respectively following structural formula to represent:
Synthesizing of (2) 1,2-phenylbenzene-1-(2'-aminophenyl) ethanol
Under nitrogen protection, 1.97g (10mmol) 2-aminobenzophenone (compd A) is dissolved in 60mL anhydrous diethyl ether, drips therein the Grignard reagent B1 solution of being prepared by 1.10g (45.8mmol) magnesium grain, 5.51g (43.5mmol) benzyl chlorine (Compound D 1) and 30mL anhydrous diethyl ether; Dropwise rear backflow 45min, add excessive methanol and ammonium nitrate cancellation reaction, washing, dry rear steaming desolventize, and recrystallizing methanol obtains faint yellow prism-shaped crystal amino alcohol product 2.60g, and yield is 89.8%.
Structural Identification:
Mass spectrum (MS m/z): 289.1 (M
+)
Ultimate analysis: C20H19NO
Theoretical value: C, 83.01; H, 6.62; N, 4.84; O, 5.53;
Measured value: C, 83.05; H, 6.58; N, 4.81; O, 5.56.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1,2-phenylbenzene-1-(2'-aminophenyl) ethanol.
(3) cyclic metal complexes 3,4-phenylbenzene cinnolines synthetic
100 ℃ of heating 45min in the sulfuric acid that the amino alcohol product that the upper step reaction of 0.75g (2.6mmol) is made is 20% in 20mL volume fraction, are adjusted to weakly alkaline with ammoniacal liquor; After extracted with diethyl ether, steam and desolventize, add 5mL acetic acid and 3.5mL concentrated hydrochloric acid, after dissolving completely, the aqueous solution that to add containing Sodium Nitrite volume fraction be 2.5%, adds ammoniacal liquor and is adjusted to weakly alkaline after 30min; Chloroform extraction, recrystallizing methanol, obtains tawny tabular crystal 0.42g, and yield is 57.2%.
Structural Identification:
Mass spectrum (MS m/z): 282.1 (M
+)
Ultimate analysis: C20H14N2
Theoretical value: C, 85.08; H, 5.00; N, 9.92;
Measured value: C, 85.00; H, 5.05; N, 9.95.
The resulting material of the above-mentioned reaction of above data acknowledgement is 3,4-phenylbenzene cinnolines.
(4) main part is the dimeric synthetic containing iridium dichloro of 3,4-phenylbenzene cinnolines
By 0.20g (0.56mmol) three hydration iridous chlorides, 0.47g (1.68mmol) 3,4-phenylbenzene cinnolines, ethoxy ethanol that 20mL volume ratio is 3:1 and the mixed solvent of water are put into 35mL round-bottomed flask, after solvent is degassed, use N
2protection, and under lucifuge 90 ℃ heating 20h.After being chilled to room temperature, filter, precipitation absolute ethanol washing 3 times, vacuum-drying, obtains scarlet title complex 0.34g, and yield is 76.8%, and crude product, without further purification, can directly drop in next step reaction.
(5) two [3,4-phenylbenzene cinnolines-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part of 0.40g (0.25mmol), be 3; 4-phenylbenzene cinnolines containing iridium dichloro dimer, 0.10g (1mmol) methyl ethyl diketone and 0.27g (2.5mmol) sodium carbonate are dissolved in 25mL methylene dichloride, heating mixed solution is to reflux temperature stirring reaction 12h.Be chilled to after room temperature, remove solvent under reduced pressure, the normal hexane that residuum is 6:1 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 28.1%.
Structural Identification:
Mass spectrum (MS m/z): 854.2 (M
+)
Ultimate analysis: C45H33IrN4O2
Theoretical value: C, 63.29; H, 3.89; Ir, 22.51; N, 6.56; O, 3.75;
Measured value: C, 63.23; H, 3.94; Ir, 22.55; N, 6.52; O, 3.76.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [3,4-phenylbenzene cinnolines-N, C
2'] (methyl ethyl diketone) 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), at 628nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in 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=0.41, 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 two [3-(6'-p-methoxy-phenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) 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 Grignard reagent B2 that provide respectively following structural formula to represent:
(2) 1-phenyl-1-(2'-aminophenyl)-2-(2'-p-methoxy-phenyl) ethanol is synthetic
Under nitrogen protection, 1.97g (10mmol) 2-aminobenzophenone is dissolved in 60mL anhydrous diethyl ether, drips therein the Grignard reagent B2 solution of being prepared by 1.06g (43.5mmol) magnesium grain, 6.81g (43.5mmol) O-methoxy benzyl chlorine and 30mL anhydrous diethyl ether; Dropwise rear backflow 40min, add excessive methanol and ammonium nitrate cancellation reaction, washing, dry rear steaming desolventize, and recrystallizing methanol obtains faint yellow prism-shaped crystal amino alcohol product 2.56g, and yield is 80.1%.
Structural Identification:
Mass spectrum (MS m/z): 319.2 (M
+)
Ultimate analysis: C21H21NO2
Theoretical value: C, 78.97; H, 6.63; N, 4.39; O, 10.02;
Measured value: C, 78.93; H, 6.69; N, 4.35; O, 10.04.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-phenyl-1-(2'-aminophenyl)-2-(2'-p-methoxy-phenyl) ethanol.
(3) cyclic metal complexes 3-(2'-p-methoxy-phenyl)-4-phenyl cinnolines is synthetic
100 ℃ of heating 40min in the sulfuric acid that the amino alcohol product that the upper step reaction of 0.83g (2.6mmol) is made is 20% in 20mL volume fraction, are adjusted to weakly alkaline with ammoniacal liquor; After extracted with diethyl ether, steam and desolventize, add 5mL acetic acid and 3.5mL concentrated hydrochloric acid, after dissolving completely, the aqueous solution that to add containing Sodium Nitrite volume fraction be 2.5%, adds ammoniacal liquor and is adjusted to weakly alkaline after 33min; Chloroform extraction, recrystallizing methanol, obtains tawny tabular crystal 0.37g, and yield is 45.6%.
Structural Identification:
Mass spectrum (MS m/z): 312.1 (M
+)
Ultimate analysis: C21H16N2O
Theoretical value: C, 80.75; H, 5.16; N, 8.97; O, 5.12;
Measured value: C, 80.70; H, 5.23; N, 8.92; O, 5.15.
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(2'-p-methoxy-phenyl)-4-phenyl cinnolines.
(4) main part is the dimeric synthetic containing iridium dichloro of 3-(2'-p-methoxy-phenyl)-4-phenyl cinnolines
0.20g (0.56mmol) three hydration iridous chlorides, 0.44g (1.4mmol) 3-(2'-p-methoxy-phenyl)-4-phenyl cinnolines, ethoxy ethanol that 30mL volume ratio is 3:1 and the mixed solvent of water are put into 50mL round-bottomed flask, after solvent is degassed, use N
2protection, and under lucifuge 90 ℃ heating 24h.After being chilled to room temperature, filter, precipitation absolute ethanol washing 3 times, vacuum-drying, obtains scarlet title complex 0.31g, and yield is 65.1%, and crude product, without further purification, can directly drop in next step reaction.
(5) two [3-(6'-p-methoxy-phenyl)-4-phenyl cinnolines-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part of 0.42g (0.25mmol) be 3-(2'-p-methoxy-phenyl)-4-phenyl cinnolines containing iridium dichloro dimer; 0.08g (0.75mmol) methyl ethyl diketone and 0.21g (2mmol) sodium carbonate are dissolved in 20mL trichloromethane, and heating mixed solution is to reflux temperature stirring reaction 10h.Be chilled to after room temperature, remove solvent under reduced pressure, the normal hexane that residuum is 8:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel.Collect red part, steaming desolventizes, and after being dried, obtains 0.11g pure products, and yield is 24.1%.
Structural Identification:
Mass spectrum (MS m/z): 914.2 (M
+)
Ultimate analysis: C47H37IrN4O4
Theoretical value: C, 61.76; H, 4.08; Ir, 21.03; N, 6.13; O, 7.00;
Measured value: C, 61.73; H, 4.14; Ir, 21.05; N, 6.06; O, 7.02.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [3-(6'-p-methoxy-phenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 634nm 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 3: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex two [3-(5'-ethoxyl phenenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) 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 Grignard reagent B3 that provide respectively following structural formula to represent:
(2) 1-phenyl-1-(2'-aminophenyl)-2-(3'-ethoxyl phenenyl) ethanol is synthetic
Under nitrogen protection, 1.97g (10mmol) 2-aminobenzophenone is dissolved in 60mL anhydrous diethyl ether, drips therein the Grignard reagent B3 solution of being prepared by 1.10g (45.8mmol) magnesium grain, 7.42g (43.5mmol) m-oxethyl benzyl chlorine and 30mL anhydrous diethyl ether; Dropwise rear backflow 50min, add excessive methanol and ammonium nitrate cancellation reaction, washing, dry rear steaming desolventize, and recrystallizing methanol obtains faint yellow prism-shaped crystal amino alcohol product 2.83g, and yield is 84.9%.
Structural Identification:
Mass spectrum (MS m/z): 333.2 (M
+)
Ultimate analysis: C22H23NO2
Theoretical value: C, 79.25; H, 6.95; N, 4.20; O, 9.60;
Measured value: C, 79.21; H, 6.99; N, 4.26; O, 9.54.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-phenyl-1-(2'-aminophenyl)-2-(3'-ethoxyl phenenyl) ethanol.
(3) 3-(3'-ethoxyl phenenyl)-4-phenyl cinnolines is synthetic
100 ℃ of heating 50min in the sulfuric acid that the amino alcohol product that the upper step reaction of 0.87g (2.6mmol) is made is 20% in 20mL volume fraction, are adjusted to weakly alkaline with ammoniacal liquor; After extracted with diethyl ether, steam and desolventize, add 5mL acetic acid and 3.5mL concentrated hydrochloric acid, after dissolving completely, the aqueous solution that to add containing Sodium Nitrite volume fraction be 2.5%, adds ammoniacal liquor and is adjusted to weakly alkaline after 35min; Chloroform extraction, recrystallizing methanol, obtains tawny tabular crystal 0.41g, and yield is 48.3%.
Structural Identification:
Mass spectrum (MS m/z): 326.1 (M
+)
Ultimate analysis: C22H18N2O
Theoretical value: C, 80.96; H, 5.56; N, 8.58; O, 4.90;
Measured value: C, 80.93; H, 5.62; N, 8.54; O, 4.91.
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(3'-ethoxyl phenenyl)-4-phenyl cinnolines.
(4) main part is the dimeric synthetic containing iridium dichloro of 3-(3'-ethoxyl phenenyl)-4-phenyl cinnolines
0.20g (0.56mmol) three hydration iridous chlorides, 0.37g (1.12mmol) 3-(2'-ethoxyl phenenyl)-4-phenyl cinnolines, ethoxy ethanol that 40mL volume ratio is 3:1 and the mixed solvent of water are put into 100mL round-bottomed flask, after solvent is degassed, use N
2protection, and under lucifuge 90 ℃ heating 22h.After being chilled to room temperature, filter, precipitation absolute ethanol washing 3 times, vacuum-drying, obtains scarlet title complex 0.34g, and yield is 69.1%, and crude product, without further purification, can directly drop in next step reaction.
(5) two [3-(5'-ethoxyl phenenyl)-4-phenyl cinnolines-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part of 0.44g (0.25mmol) be 3-(3'-ethoxyl phenenyl)-4-phenyl cinnolines containing iridium dichloro dimer; 0.09g (0.875mmol) methyl ethyl diketone and 0.41g (3mmol) salt of wormwood are dissolved in 30mL1; 2-ethylene dichloride, heating mixed solution is to reflux temperature stirring reaction 8h.Be chilled to after room temperature, remove solvent under reduced pressure, the normal hexane that residuum is 10:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel.Collect red part, steaming desolventizes, and after being dried, obtains 0.11g pure products, and yield is 23.3%.
Structural Identification:
Mass spectrum (MS m/z): 942.3 (M
+)
Ultimate analysis: C49H41IrN4O4
Theoretical value: C, 62.47; H, 4.39; Ir, 20.40; N, 5.95; O, 6.79;
Measured value: C, 62.42; H, 4.46; Ir, 20.33; N, 5.98; O, 6.81.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [3-(5'-ethoxyl phenenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 634nm 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 4: a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex two [3-(4'-butoxy phenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) 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 Grignard reagent B4 that provide respectively following structural formula to represent:
(2) 1-phenyl-1-(2'-aminophenyl)-2-(4'-butoxy phenyl) ethanol is synthetic
Under nitrogen protection, 1.97g (10mmol) 2-aminobenzophenone is dissolved in 60mL anhydrous diethyl ether, drips therein the Grignard reagent B4 solution of by 1.16g (47.85mmol) magnesium grain, 8.64g (43.5mmol) being prepared by butoxy benzyl chlorine and 30mL anhydrous diethyl ether; Dropwise rear backflow 45min, add excessive methanol and ammonium nitrate cancellation reaction, washing, dry rear steaming desolventize, and recrystallizing methanol obtains faint yellow prism-shaped crystal amino alcohol product 3.14g, and yield is 86.9%.
Structural Identification:
Mass spectrum (MS m/z): 361.2 (M
+)
Ultimate analysis: C24H27NO2
Theoretical value: C, 79.74; H, 7.53; N, 3.87; O, 8.85;
Measured value: C, 79.70; H, 7.59; N, 3.84; O, 8.87.
The resulting material of the above-mentioned reaction of above data acknowledgement is 1-phenyl-1-(2'-aminophenyl)-2-(4'-butoxy phenyl) ethanol.
(3) 3-(4'-butoxy phenyl)-4-phenyl cinnolines is synthetic
100 ℃ of heating 45min in the sulfuric acid that the amino alcohol product that the upper step reaction of 0.94g (2.6mmol) is made is 20% in 20mL volume fraction, are adjusted to weakly alkaline with ammoniacal liquor; After extracted with diethyl ether, steam and desolventize, add 5mL acetic acid and 3.5mL concentrated hydrochloric acid, after dissolving completely, the aqueous solution that to add containing Sodium Nitrite volume fraction be 2.5%, adds ammoniacal liquor and is adjusted to weakly alkaline after 30min; Chloroform extraction, recrystallizing methanol, obtains tawny tabular crystal 0.47g, and yield is 51.0%.
Structural Identification:
Mass spectrum (MS m/z): 354.2 (M
+)
Ultimate analysis: C24H22N2O
Theoretical value: C, 81.33; H, 6.26; N, 7.90; O, 4.51;
Measured value: C, 81.27; H, 6.33; N, 7.84; O, 4.56.
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(4'-butoxy phenyl)-4-phenyl cinnolines.
(4) main part is the dimeric synthetic containing iridium dichloro of 3-(4'-butoxy phenyl)-4-phenyl cinnolines
0.20g (0.56mmol) three hydration iridous chlorides, 0.50g (1.4mmol) 3-(4'-butoxy phenyl)-4-phenyl cinnolines, ethoxy ethanol that 35mL volume ratio is 3:1 and the mixed solvent of water are put into 50mL round-bottomed flask, after solvent is degassed, use N
2protection, and under lucifuge 90 ℃ heating 24h.After being chilled to room temperature, filter, precipitation absolute ethanol washing 3 times, vacuum-drying, obtains scarlet title complex 0.38g, and yield is 72.6%, and crude product, without further purification, can directly drop in next step reaction.
(5) two [3-(4'-butoxy phenyl)-4-phenyl cinnolines-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part of 0.47g (0.25mmol) be 3-(4'-aminomethyl phenyl)-4-phenyl cinnolines containing iridium dichloro dimer; 0.10g (1mmol) methyl ethyl diketone and 0.28g (2.0mmol) salt of wormwood are dissolved in 25mL2-ethoxy ethanol, and heating mixed solution is to reflux temperature stirring reaction 5h.Be chilled to after room temperature, remove solvent under reduced pressure, the normal hexane that residuum is 12:1 by volume ratio and ethyl acetate mixed solvent column chromatography on silica gel.Collect red part, steaming desolventizes, and after being dried, obtains 0.10g pure products, and yield is 20.0%.
Structural Identification:
Mass spectrum (MS m/z): 998.2 (M
+)
Ultimate analysis: C53H49IrN4O4
Theoretical value: C, 63.77; H, 4.95; Ir, 19.26; N, 5.61; O, 6.41;
Measured value: C, 63.71; H, 4.97; Ir, 19.33; N, 5.56; O, 6.43.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [3-(4'-butoxy phenyl)-4-phenyl cinnolines-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 626nm 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=0.23.
Embodiment 5:
The title complex two [3-(6'-aminomethyl phenyl)-4-phenyl cinnolines-N, the C that with embodiment 1, make
2'] (methyl ethyl diketone) close iridium as the organic electroluminescence device of 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, by vacuum evaporation, on anode 301, prepare successively 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, two [3-(6'-aminomethyl phenyl)-4-phenyl cinnolines-N with a layer thickness embodiment that is 8% doped with massfraction 1 preparation that is 30nm, C
2'] (methyl ethyl diketone) 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) LiF that the Alq3 that material is 20nm as hole blocking layer 305, thickness (three (oxine) aluminium) 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.
Through performance test, know, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 633nm, and maximum current efficiency is 18.0cd/A, and maximum external quantum efficiency is 9.5%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications 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), with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, also comprises assistant ligand, and described assistant ligand is methyl ethyl diketone, in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
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 Grignard reagent B that provide following structural formula to represent:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(2) under protection of inert gas, compd A is dissolved in organic solvent, then drips wherein the anhydrous ether solution of Grignard reagent B; after dropwising; reflux 40～45 minutes, then add methyl alcohol and ammonium nitrate quencher reaction, after separation and purification, obtain the Compound C that following structural formula represents:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(3) in the sulfuric acid that is 20% by described Compound C in volume fraction, 100 ℃ are heated 40～50 minutes, add again ammoniacal liquor to regulate pH to 8～9, extracted with diethyl ether obtains one-level product after steaming and desolventizing, gained one-level product is dissolved in acetic acid and concentrated hydrochloric acid mixing solutions, add again sodium nitrite in aqueous solution, after 30～35 minutes, add ammoniacal liquor to regulate pH to 8～9, after separation and purification, obtain cyclic metal complexes;
(4) under protection of inert gas, by the cyclic metal complexes obtaining in step (3) and hydration iridous chloride with mol ratio 2～3:1 in the mixed solvent of cellosolvo and water, be heated to 90 ℃ and carry out polyreaction 20～24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is:
Wherein, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group;
(5) under protection of inert gas and alkali condition; the chlorine bridge dipolymer obtaining in step (4) and methyl ethyl diketone are heated to reflux in the second organic solvent 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); with 3; 4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes; also comprise assistant ligand; described assistant ligand is methyl ethyl diketone; in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
3. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, the anhydrous ether solution of described Grignard reagent B obtains by following manner: magnesium grain, Compound D are joined in anhydrous diethyl ether, fully stir, the structural formula of described Compound D is:
In formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group.
4. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, is characterized in that, in step (4), the concentration of described hydration iridous chloride in the mixed solvent of cellosolvo and water is 0.014～0.028mol/L.
5. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, in step (5), described the second organic solvent is cellosolvo, 2-methyl cellosolve, methylene dichloride, 1,2-ethylene dichloride or trichloromethane.
6. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, the described purification procedures of step (2) comprising: after completion of the reaction, cooling reaction solution is to room temperature, product adopts distilled water to wash, dry, and obtain Compound C crude product after steaming solvent.
7. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, the described purification procedures of step (3) comprising: first adopt chloroform extraction, then adopt methyl alcohol to carry out recrystallization, obtain the cyclic metal complexes after purifying.
8. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, the described purification procedures of step (4) comprising: after 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 ruddiness organic electromechanical phosphorescent material iridium metal complex as claimed in claim 2, it is characterized in that, step (5) further comprises the steps: after completion of the reaction, after steaming solvent, the method for employing underpressure distillation obtains iridium metal complex crude product, the normal hexane that is 6～12:1 by volume ratio again and ethyl acetate mixed solvent carry out silica gel column chromatography, 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 is as the formula (1), with 3,4-phenylbenzene cinnolines or derivatives thereof is cyclic metal complexes, also comprises assistant ligand, and described assistant ligand is methyl ethyl diketone, in formula, R is hydrogen atom or C
1～C
4straight or branched alkoxyl group,
The structural formula of described cyclic metal complexes is:
or
wherein, n=1～4.
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| EP3398953A1 (en) * | 2017-05-05 | 2018-11-07 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN114478637A (en) * | 2020-10-23 | 2022-05-13 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3398953A1 (en) * | 2017-05-05 | 2018-11-07 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US10862055B2 (en) | 2017-05-05 | 2020-12-08 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN114478637A (en) * | 2020-10-23 | 2022-05-13 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
| CN114478641A (en) * | 2020-10-23 | 2022-05-13 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
| CN114478640A (en) * | 2020-10-23 | 2022-05-13 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
| CN114478637B (en) * | 2020-10-23 | 2023-09-05 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
| CN114478641B (en) * | 2020-10-23 | 2023-09-05 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
| CN114478640B (en) * | 2020-10-23 | 2023-10-24 | 北京绿人科技有限责任公司 | Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device |
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