CN104059628A - Organic phosphorescence material and preparation method thereof and organic electroluminescent device - Google Patents
Organic phosphorescence material and preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention provides an organic phosphorescence material shown in a structural formula (I), in the formula, R is amino, dimethylamino or dibenzyl amino, X and Y are respectively C1 or F, or X and Y are same as C1. According to the invention, a compound A and tri(acetylacetone)iridium are reacted under anhydrous anoxic condition to obtain the organic phosphorescence material shown in the structural formula (I). The material can obtain good energy transfer efficiency and appropriate blue light emission wavelength, and can be widely used for preparing the blue light electroluminescent device, so that the device has good luminescence performance.
Description
Technical field
The invention belongs to luminous organic material field, be specifically related to a kind of organic phosphorescent material and preparation method thereof and organic electroluminescence device.
Background technology
Organic phosphorescent 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 phosphor 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 can 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, better and the most frequently used blue light organic phosphorescent electroluminescent materials of over-all properties has iridium metal complex [two (2 ', 4 '-difluorophenyl) pyridine] (2-pyridine carboxylic acid) close iridium (FIrpic), [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] closes iridium (FIr6), [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium (FIrN4) etc.Yet current blue phosphorescent material is Shortcomings aspect the efficiency decay of illuminant colour purity, luminous efficiency and device, and stability is not good, the life-span is short.
Summary of the invention
For overcoming the problem of above-mentioned prior art, the invention provides a kind of organic phosphorescent material and preparation method thereof and organic electroluminescence device.In a kind of organic phosphorescent material molecule provided by the invention, contain bipyridine ligand, on a pyridine ring, with two halogen radicals, and on another pyridine ring, introduce amino or substituted-amino, there is higher luminous quantum efficiency, also can make the effective blue shift of emission 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 blue light, and has good luminescent properties.
On the one hand, the invention provides a kind of organic phosphorescent material, in described organic phosphorescent material molecule, contain bipyridine ligand, as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
In above-mentioned organic phosphorescent material molecule, contain bipyridine ligand, on a pyridine ring, with two halogen radicals (F or Cl), strong electron-withdrawing substituent is rolled into a ball blue shift emission wavelength effectively, improves luminescent properties.And, on another pyridine ring, introduce amino or substituted-amino, make absorption peak blue shift, thereby obtain good energy transmission efficiency and suitable blue light emitting wavelength.
Second aspect, the invention provides a kind of preparation method of organic phosphorescent material, comprises the following steps:
The compd A and the compd B that provide respectively following structural formula to represent:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl;
Under anhydrous and oxygen-free condition, according to mol ratio 3:1～5:1, compd A and compd B are dissolved in the first organic solvent and are reacted, be heated to reflux and react 20～30h, after separation and purification, obtain the organic phosphorescent material as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
The reaction formula of described reaction is as follows:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
Compd B is that tri acetylacetonato closes iridium (Ir (acac)
3).
Preferably, the first organic solvent that reaction adopts is ethylene glycol, glycerine, DMF, cellosolvo or 2-methoxyl group methyl alcohol.
Preferably, the concentration of compd B in the first organic solvent is 0.01～0.1mol/L.
After question response 20～30h, carry out separation and purification and can obtain described organic phosphorescent material.Particularly, separation and purification comprises following operation steps: question response liquid naturally cools to room temperature, to the HCl aqueous solution, the ether that drip 1mol/L in reaction solution, repeatedly extracts, and merges organic phase, with anhydrous magnesium sulfate drying; Then filter, rotation steaming removes filtrate solvent and obtains crude product; Finally take methylene dichloride as elutriant carries out silica gel column chromatography separation to this crude product, obtain the described organic phosphorescent material of purifying.
Preferably, compd A can make by the following method:
The Compound C and the Compound D that provide respectively following structural formula to represent:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
In nitrogen or atmosphere of inert gases, according to mol ratio 1:1～1:2, Compound C and Compound D are dissolved in the second organic solvent, add again catalyzer and alkali, be heated to reflux and carry out Suzuki linked reaction 24～30h, after separation and purification, obtain the compd A as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
The reaction formula of described Suzuki linked reaction is as follows:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
Preferably, the second organic solvent that Suzuki linked reaction adopts is toluene, DMF (DMF), Isosorbide-5-Nitrae-dioxane or dimethylbenzene.
The consumption of organic solvent is enough, so that each reactants dissolved fully reaction.Preferably, the concentration of Compound C in the second organic solvent is 0.1～0.2mol/L.
The mole dosage of the catalyzer that preferably, Suzuki linked reaction adopts is 1%～5% of Compound C mole dosage.Preferably, catalyzer is that four (triphenyl phosphorus) close palladium (Pd (PPh
3)
4) or two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2).
The alkali that Suzuki linked reaction adopts can be inorganic alkali solution, and inorganic alkali solution can be the aqueous solution of alkali metal hydroxide or alkaline carbonate.Preferably, alkali be in wet chemical and the barium hydroxide octahydrate aqueous solution one or both.
Preferably, the mole dosage of alkali is 2～5 times of Compound C mole dosage.
After Suzuki linked reaction 24～30h, carry out separation and purification and can obtain described compd A.Particularly, separation and purification comprises following operation steps: distilled water, ethyl acetate for reaction solution are repeatedly extracted to rear merging organic phase, then use anhydrous magnesium sulfate drying, filter, rotation is steamed and desolventized to obtain crude product; Finally with the mixed solution of ethyl acetate and normal hexane, make eluent, crude product is carried out to silica gel column chromatography separation, obtain the described compd A of purifying.
Preferably, separation and purification is carried out according to following operation steps: question response liquid naturally cools to room temperature, and rotation is steamed and desolventized, and adds methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized; Finally with the mixed solution of ethyl acetate and normal hexane, make eluent, crude product is carried out to silica gel column chromatography separation, obtain the described compd A of purifying.
In above steps reaction, the reacting weight of each reactant can be to carry out proportioning according to the metering ratio shown in chemical equation, can be also that partial reaction thing is excessive, can carry out the preparation method of the present embodiment, and does not affect reaction and carry out.
The preparation method of above-mentioned organic phosphorescent material adopts 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 the organic phosphorescent material making has higher luminous quantum efficiency, there is very wide commercialized development prospect.
The third aspect, the invention provides a kind of organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that the organic phosphorescent material having adulterated as described in first aspect present invention in described luminescent layer.
In above-mentioned organic phosphorescent material molecule, contain bipyridine ligand, on a pyridine ring, with two halogen radicals (F or Cl), strong electron-withdrawing substituent is rolled into a ball blue shift emission wavelength effectively, improves luminescent properties.And, on another pyridine ring, introduce amino or substituted-amino, make absorption peak blue shift, thereby obtain good energy transmission efficiency and suitable blue light emitting wavelength.The preparation method of above-mentioned organic phosphorescent material adopts 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 the organic phosphorescent material making has higher luminous quantum efficiency, there is very wide commercialized development prospect.In above-mentioned organic electroluminescence device, the above-mentioned organic phosphorescent material of usining is doped in the material of main part in organic electroluminescence device luminescent layer as guest materials, has good consistency, can be widely used in and prepare blue light electroluminescent device.The organic electroluminescence device of above-mentioned organic phosphorescent material of having adulterated in luminescent layer can be launched high purity blue light, 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 utilizing emitted light spectrogram of organic phosphorescent material in the embodiment of the present invention 1;
Fig. 2 is the structural representation of organic electroluminescence device in the embodiment of the present invention 10.
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.
Embodiment 1: a kind of organic phosphorescent material title complex three (2 ', 6 '-bis-chloro-4-amino-2,3 '-dipyridyl-N, C2 ') closes iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 1 and the Compound D 1 that provide respectively following structural formula to represent:
(2) 2,6-bis-are chloro-4 '-amino-3,2 '-dipyridyl synthetic
Under nitrogen protection, (1.04g, 6.00mmol) 4-amino-2-bromopyridine, (1.38g, 7.20mmol) 2,6-bis-chloro-3-pyridyl boric acid, (0.35g, 0.30mmol) Pd (PPh
3)
4be dissolved in after 30mL toluene, adding 22mmol massfraction is 5% K
2cO
3the aqueous solution, is heated to reflux, stirring reaction 24h.Be chilled to after room temperature, add distilled water, and with 100mL ethyl acetate extraction 3 times, merge organic phase, anhydrous magnesium sulfate drying.Filter, remove solvent under reduced pressure and obtain crude product.The ethyl acetate that the volume ratio of take is 1:6 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain colorless solid product 0.86g, and yield is 59.7%.
Product detects data:
Mass spectrum (m/z): 239.0 (M
++ 1)
Ultimate analysis: C
10h
7cl
2n
3
Theoretical value: C, 50.03; H, 2.94; Cl, 29.53; N, 17.50;
Measured value: C, 50.05; H, 2.93; Cl, 29.52; N, 17.50.
(3) title complex three (2 ', 6 '-bis-chloro-4-amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, (3.60g, 15.00mmol) 2, the chloro-4 '-amino-3 of 6-bis-, 2 '-dipyridyl and (1.83g, 3.75mmol) tri acetylacetonato close iridium and are dissolved in 50mL ethylene glycol, are heated to reflux state, stirring reaction 30h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.61g, yield is 17.9%.
Product detects data:
Mass spectrum (m/z): 908.9 (M
++ 1)
Ultimate analysis: C
30h
18cl
6irN
9
Theoretical value: C, 39.62; H, 1.99; Cl, 23.39; Ir, 21.14; N, 13.86;
Measured value: C, 39.60; H, 1.98; Cl, 23.40; Ir, 21.15; N, 13.87.
Fig. 1 is the utilizing emitted light spectrogram of the organic phosphorescent material that makes of the embodiment of the present invention 1.As shown in Figure 1, transverse axis is wavelength (Wavelength, the nm of unit), and the longitudinal axis is standardized photoluminescence intensity (NormalizedPL intensity), and at 298K temperature, (concentration is 10 to title complex
-5mol/L) at CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 450nm place, has an acromion at 475nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 2: a kind of organic phosphorescent material title complex three (2 '-fluoro-6 '-chloro-4-amino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 2 and the Compound D 2 that provide respectively following structural formula to represent:
(2) chloro-4 '-amino-2 ', the 3-dipyridyl of the fluoro-6-of 2-is synthetic
Under nitrogen protection, (1.04g, 6.00mmol) 4-amino-2-bromopyridine, the fluoro-6-chloro-3-pyridyl of (1.58g, 9.00mmol) 2-boric acid, (0.07g, 0.06mmol) Pd (PPh
3)
4be dissolved in after 60mL toluene, adding 12mmol massfraction is 5% K
2cO
3the aqueous solution, is heated to reflux, stirring reaction 24h.Be chilled to after room temperature, add distilled water, and with 100mL ethyl acetate extraction 3 times, merge organic phase, anhydrous magnesium sulfate drying.Filter, remove solvent under reduced pressure and obtain crude product.The ethyl acetate that the volume ratio of take is 1:6 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain colorless solid product 0.83g, and yield is 61.8%.
Product detects data:
Mass spectrum (m/z): 223.0 (M
++ 1)
Ultimate analysis: C
10h
7clFN
3
Theoretical value: C, 53.71; H, 3.15; Cl, 15.85; F, 8.50; N, 18.79;
Measured value: C, 53.70; H, 3.16; Cl, 15.84; F, 8.51; N, 18.79.
(3) title complex three (2 '-fluoro-6 '-chloro-4-amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, chloro-4 '-amino-2 ', the 3-dipyridyl of the fluoro-6-of (3.35g, 15.00mmol) 2-and (1.83g, 3.75mmol) tri acetylacetonato close iridium and are dissolved in 37.5mL glycerine, are heated to reflux state, stirring reaction 20h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.60g, yield is 18.6%.
Product detects data:
Mass spectrum (m/z): 859.0 (M
++ 1)
Ultimate analysis: C
30h
18cl
3f
3irN
9
Theoretical value: C, 41.89; H, 2.11; Cl, 12.37; F, 6.63; Ir, 22.35; N, 14.66;
Measured value: C, 41.86; H, 2.12; Cl, 12.38; F, 6.64; Ir, 22.37; N, 14.64.
Embodiment 3: a kind of organic phosphorescent material title complex three (2 '-chloro-6 '-fluoro-4-amino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 3 and the compound d3 that provide respectively following structural formula to represent:
(2) fluoro-4 '-amino-2 ', the 3-dipyridyl of the chloro-6-of 2-is synthetic
Under nitrogen protection, (1.04g, 6.00mmol) 4-amino-2-bromopyridine; the chloro-6-fluoro-3-pyridine of (1.58g, 9.00mmol) 2-boric acid, (0.07g; 0.06mmol) Pd (PPh3) 4 is dissolved in after 60mL DMF, and adding 12mmol massfraction is 5% K
2cO
3the aqueous solution, is heated to reflux, stirring reaction 26h.Be chilled to after room temperature, add distilled water, and with 100mL ethyl acetate extraction 3 times, merge organic phase, anhydrous magnesium sulfate drying.Filter, remove solvent under reduced pressure and obtain crude product.The ethyl acetate that the volume ratio of take is 1:6 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain colorless solid product 0.80g, and yield is 59.6%.
Product detects data:
Mass spectrum (m/z): 223.0 (M
++ 1)
Ultimate analysis: C
10h
7clFN
3
Theoretical value: C, 53.71; H, 3.15; Cl, 15.85; F, 8.50; N, 18.79;
Measured value: C, 53.73; H, 3.13; Cl, 15.87; F, 8.49; N, 18.78.
(3) title complex three (2 '-chloro-6 '-fluoro-4-amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, fluoro-4 '-amino-2 ', the 3-dipyridyl of the chloro-6-of (3.35g, 15.00mmol) 2-and (2.44g, 5.00mmol) tri acetylacetonato close iridium and are dissolved in 50mL glycerine, are heated to reflux state, stirring reaction 20h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 100mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.60g, yield is 18.6%.
Product detects data:
Mass spectrum (m/z): 859.0 (M
++ 1)
Ultimate analysis: C
30h
18cl
3f
3irN
9
Theoretical value: C, 41.89; H, 2.11; Cl, 12.37; F, 6.63; Ir, 22.35; N, 14.66;
Measured value: C, 41.87; H, 2.13; Cl, 12.35; F, 6.65; Ir, 22.33; N, 14.68.
Embodiment 4: a kind of organic phosphorescent material title complex three (2 ', 6 '-bis-chloro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 4 and the Compound D 4 that provide respectively following structural formula to represent:
(2) chloro-4 '-dimethylamino-3 of 2,6-bis-, 2 '-dipyridyl synthetic
Under nitrogen protection; 60mL is contained to (1.21g; 6.00mmol) 1 of the bromo-4-of 2-(dimethylamino) pyridine; the 4-dioxane aqueous solution (v/v=1/3) joins (2.07g is housed; 10.80mmol) 2; 6-bis-chloro-3-pyridyl boric acid, (5.68g, 18mmol) Ba (OH)
28H
2o and (0.14g, 0.12mmol) Pd (PPh
3)
4100mL single necked round bottom flask in, be heated to reflux, stirring reaction 26h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:6 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 0.96g yellow oil, and yield is 59.7%.
Product detects data:
Mass spectrum (m/z): 267.0 (M
++ 1)
Ultimate analysis: C
12h
11cl
2n
3
Theoretical value: C, 53.75; H, 4.13; Cl, 26.44; N, 15.67;
Measured value: C, 53.78; H, 4.12; Cl, 26.43; N, 15.66.
(3) title complex three (2 ', 6 '-bis-chloro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, (4.02g, 15.00mmol) 2, the chloro-4 '-amino-3 of 6-bis-, 2 '-dipyridyl and (2.44g, 5.00mmol) tri acetylacetonato close iridium and are dissolved in 100mL DMF, are heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.36g, yield is 14.9%.
Product detects data:
Mass spectrum (m/z): 993.0 (M
++ 1)
Ultimate analysis: C
36h
30cl
6irN
9
Theoretical value: C, 43.52; H, 3.04; Cl, 21.41; Ir, 19.35; N, 12.69;
Measured value: C, 43.50; H, 3.06; Cl, 21.40; Ir, 19.36; N, 12.69.
Embodiment 5: a kind of organic phosphorescent material iridium metal complex three (2 '-fluoro-6 '-chloro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 5 and the Compound D 5 that provide respectively following structural formula to represent:
(2) chloro-4 '-dimethylamino-3 of the fluoro-6-of 2-, 2 '-dipyridyl synthetic
Under nitrogen protection; 60mL is contained to (1.21g; 6.00mmol) 1 of the bromo-4-of 2-(dimethylamino) pyridine; the 4-dioxane aqueous solution (v/v=1/3) joins (1.89g is housed; 10.80mmol) the fluoro-6-chloro-3-pyridyl of 2-boric acid, (5.68g, 18mmol) Ba (OH)
28H
2o and (0.14g, 0.12mmol) Pd (PPh
3)
4100mL single necked round bottom flask in, be heated to reflux, stirring reaction 28h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 1.00g yellow oil, and yield is 66.2%.
Product detects data:
Mass spectrum (m/z): 251.1 (M
++ 1)
Ultimate analysis: C
12h
11clFN
3
Theoretical value: C, 57.26; H, 4.41; Cl, 14.09; F, 7.55; N, 16.70;
Measured value: C, 57.24; H, 4.42; Cl, 14.10; F, 7.54; N, 16.71.
(3) title complex three (2 '-fluoro-6 '-chloro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, chloro-4 '-dimethylamino-3 of the fluoro-6-of (3.53g, 14.00mmol) 2-; 2 '-dipyridyl and (1.95g; 4.00mmol) tri acetylacetonato closes iridium and is dissolved in 80mL DMF, is heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.38g, yield is 16.1%.
Product detects data:
Mass spectrum (m/z): 945.1 (M
++ 1)
Ultimate analysis: C
36h
30cl
3f
3irN
9
Theoretical value: C, 45.79; H, 3.20; Cl, 11.26; F, 6.04; Ir, 20.36; N, 13.35;
Measured value: C, 45.76; H, 3.21; Cl, 11.27; F, 6.05; Ir, 20.34; N, 13.37.
Embodiment 6: a kind of organic phosphorescent material title complex three (2 '-chloro-6 '-fluoro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 6 and the Compound D 6 that provide respectively following structural formula to represent:
(2) chloro-4 '-dimethylamino-3 of the fluoro-6-of 2-, 2 '-dipyridyl synthetic
Under nitrogen protection; 40mL is contained to (1.21g; 6.00mmol) 1 of the bromo-4-of 2-(dimethylamino) pyridine; the 4-dioxane aqueous solution (v/v=1/3) joins (2.10g is housed; 12.00mmol) the fluoro-6-chloro-3-pyridyl of 2-boric acid, (7.57g, 24mmol) Ba (OH)
28H
2o and (0.56g, 0.18mmol) Pd (PPh
3)
2cl
2100mL single necked round bottom flask in, be heated to reflux, stirring reaction 28h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 0.95g yellow oil, and yield is 62.9%.
Product detects data:
Mass spectrum (m/z): 251.1 (M
++ 1)
Ultimate analysis: C
12h
11clFN
3
Theoretical value: C, 57.26; H, 4.41; Cl, 14.09; F, 7.55; N, 16.70;
Measured value: C, 57.23; H, 4.43; Cl, 14.08; F, 7.56; N, 16.71.
(3) title complex three (2 '-chloro-6 '-fluoro-4-dimethylamino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, fluoro-4 '-dimethylamino-3 of the chloro-6-of (3.53g, 14.00mmol) 2-; 2 '-dipyridyl and (1.95g; 4.00mmol) tri acetylacetonato closes iridium and is dissolved in 50mL2-ethoxy ethanol, is heated to reflux state, stirring reaction 28h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.40g, yield is 16.9%.
Product detects data:
Mass spectrum (m/z): 945.1 (M
++ 1)
Ultimate analysis: C
36h
30cl
3f
3irN
9
Theoretical value: C, 45.79; H, 3.20; Cl, 11.26; F, 6.04; Ir, 20.36; N, 13.35;
Measured value: C, 45.75; H, 3.22; Cl, 11.28; F, 6.01; Ir, 20.37; N, 13.37.
Embodiment 7: a kind of organic phosphorescent material title complex three (2 ', 6 '-bis-chloro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 7 and the Compound D 7 that provide respectively following structural formula to represent:
(2) chloro-4 '-diphenyl amino-3 of 2,6-bis-, 2 '-dipyridyl synthetic
Under nitrogen protection, 40mL is joined and (2.30g, 12.00mmol) 2 is housed, the chloro-4-pyridine of 6-bis-boric acid, (7.57g, 24mmol) Ba (OH) containing the dimethylbenzene of the bromo-4-of (1.95g, 6mmol) 2-(diphenyl amino) pyridine
28H
2o and (0.56g, 0.18mmol) Pd (PPh
3)
2cl
2100mL single necked round bottom flask in, be heated to reflux, stirring reaction 30h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 1.08g yellow oil, and yield is 55.1%.
Product detects data:
Mass spectrum (m/z): 391.1 (M
++ 1)
Ultimate analysis: C
22h
15cl
2n
3
Theoretical value: C, 67.36; H, 3.85; Cl, 18.08; N, 10.71;
Measured value: C, 67.34; H, 3.87; Cl, 18.05; N, 10.74.
(3) title complex three (2 ', 6 '-bis-chloro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, (3.92g, 10.00mmol) 2; chloro-4 '-diphenyl amino-3 of 6-bis-, 2 '-dipyridyl and (0.98g, 2.00mmol) tri acetylacetonato close iridium and are dissolved in 25mL2-ethoxy ethanol; be heated to reflux state, stirring reaction 28h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.48g, yield is 14.1%.
Product detects data:
Mass spectrum (m/z): 1365.1 (M
++ 1)
Ultimate analysis: C
66h
42cl
6irN
9
Theoretical value: C, 58.03; H, 3.10; Cl, 15.57; Ir, 14.07; N, 9.23;
Measured value: C, 58.05; H, 3.06; Cl, 15.58; Ir, 14.06; N, 9.25.
Embodiment 8: a kind of organic phosphorescent material title complex three (2 '-fluoro-6 '-chloro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 8 and the Compound D 8 that provide respectively following structural formula to represent:
(2) chloro-4 '-diphenyl amino-3 of the fluoro-6-of 2-, 2 '-dipyridyl synthetic
Under nitrogen protection; 40mL is contained to (1.90g; 6.00mmol) dimethylbenzene of the bromo-4-of 2-(dimethylamino) pyridine joins the fluoro-6-chloro-3-pyridyl of (1.05g, 6.00mmol) 2-boric acid, (3.79g, 15mmol) Ba (OH) is housed
28H
2the K that O, 15mmol massfraction are 5%
2cO
3the aqueous solution and (0.75g, 0.24mmol) Pd (PPh
3)
2cl
2100mL single necked round bottom flask in, be heated to reflux, stirring reaction 30h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying, and rotation is steamed and desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 1.28g yellow oil, and yield is 56.8%.
Product detects data:
Mass spectrum (m/z): 375.1 (M
++ 1)
Ultimate analysis: C
22h
15clFN
3
Theoretical value: C, 70.31; H, 4.02; Cl, 9.43; F, 5.06; N, 11.18;
Measured value: C, 70.30; H, 4.03; Cl, 9.44; F, 5.06; N, 11.17.
(3) title complex three (2 '-fluoro-6 '-chloro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, chloro-4 '-diphenyl amino-3 of the fluoro-6-of (3.75g, 10.00mmol) 2-; 2 '-dipyridyl and (0.98g; 2.00mmol) tri acetylacetonato closes iridium and is dissolved in 200mL2-methoxyl group methyl alcohol, is heated to reflux state, stirring reaction 30h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.56g, yield is 17.0%.
Product detects data:
Mass spectrum (m/z): 1315.2 (M
++ 1)
Ultimate analysis: C
66h
42cl
3f
3irN
9
Theoretical value: C, 60.21; H, 3.22; Cl, 8.08; F, 4.33; Ir, 14.60; N, 9.57;
Measured value: C, 60.20; H, 3.20; Cl, 8.10; F, 4.34; Ir, 14.63; N, 9.54.
Embodiment 9: a kind of organic phosphorescent material title complex three (2 '-chloro-6 '-fluoro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close iridium, as shown in following structural formula:
The preparation method of above-mentioned organic phosphorescent material, comprises the steps:
(1) Compound C 9 and the Compound D 9 that provide respectively following structural formula to represent:
(2) chloro-4 '-diphenyl amino-3 of the fluoro-6-of 2-, 2 '-dipyridyl synthetic
40mL is contained to (1.95g, 6.00mmol) 1 of the bromo-4-of 2-(diphenyl amino) pyridine, the 4-dioxane aqueous solution (v/v=1/3) joins the fluoro-6-chloro-3-pyridyl of (1.05g, 6.00mmol) 2-boric acid, (3.79g, 15mmol) Ba (OH) is housed
28H
2the K that O, 15mmol massfraction are 5%
2cO
3the aqueous solution and (0.75g, 0.24mmol) Pd (PPh
3)
2cl
2100mL single necked round bottom flask in, be heated to reflux, stirring reaction 24h.Be chilled to after room temperature, rotation is steamed and is desolventized, and adds 30mL methylene dichloride, and impurity screening, gets organic phase, uses saturated common salt water washing, filters, then uses anhydrous sodium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain 1.31g yellow oil, and yield is 58.1%.
Product detects data:
Mass spectrum (m/z): 375.1 (M
++ 1)
Ultimate analysis: C
22h
15clFN
3
Theoretical value: C, 70.31; H, 4.02; Cl, 9.43; F, 5.06; N, 11.18;
Measured value: C, 70.30; H, 4.03; Cl, 9.43; F, 5.07; N, 11.17.
(3) title complex three (2 '-chloro-6 '-fluoro-4-diphenyl amino-2,3 '-dipyridyl-N, C
2') close synthesizing of iridium
Under nitrogen protection, fluoro-4 '-diphenyl amino-3 of the chloro-6-of (3.76g, 10.00mmol) 2-; 2 '-dipyridyl and (1.22g; 2.50mmol) tri acetylacetonato closes iridium and is dissolved in 200mL2-methoxyl group methyl alcohol, is heated to reflux state, stirring reaction 30h.Naturally be chilled to after room temperature, progressively drip the 1mol/L HCl aqueous solution, 20mL extracted with diethyl ether 3 times.Merge organic phase, anhydrous MgSO
4dry.Filter, after filtrate rotation steaming is desolventized, take methylene dichloride as elutriant carries out silica gel column chromatography separation, obtain resulting composite 0.59g, yield is 18.0%.
Product detects data:
Mass spectrum (m/z): 1315.2 (M
++ 1)
Ultimate analysis: C
66h
42cl
3f
3irN
9
Theoretical value: C, 60.21; H, 3.22; Cl, 8.08; F, 4.33; Ir, 14.60; N, 9.57;
Measured value: C, 60.23; H, 3.20; Cl, 8.09; F, 4.32; Ir, 14.62; N, 9.55.
Embodiment 10:
The title complex three making with embodiment 1 (2 ', 6 '-bis-chloro-4-amino-2,3 '-dipyridyl-N, C
2') close iridium as the organic electroluminescence device of luminescent layer doping object, structure as shown in Figure 2:
This device is followed successively by ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%Ir title complex (30nm)/BCP (10nm)/Alq
3(35nm)/LiF (1nm)/Al (120nm), on a glass substrate, deposit a layer thickness and be 100nm, square resistance and be the tin indium oxide (ITO) of 10～20 Ω/mouths as transparent anode, by vacuum evaporation technology, on ITO, to prepare successively m-MTDATA hole-injecting material that a layer thickness is 40nm, NPB hole mobile material that a layer thickness is 20nm, mCP electronic barrier layer, a layer thickness that a layer thickness is 10nm be 30nm doped with three (2 ' of 7wt% embodiment 1 preparation, 6 '-bis-chloro-4-amino-2,4 '-dipyridyl-N, C
2') close the mCP luminescent layer of iridium, the BCP hole blocking layer that a layer thickness is 10nm, the Alq that a layer thickness is 35nm
3the LiF electronic injection buffer layer that electron transfer layer, a layer thickness are 1nm, the last metal A l that vacuum plating deposit thickness is 120nm on buffer layer is as the negative electrode of device.
Test component 1 is (500cd/m under 9V voltage drives
2) electroluminescent spectrum, obtaining maximum emission wavelength is 465nm, 489nm has acromion, device external quantum efficiency is 4.8%, luminous efficiency is 5.4lm/W.
This organic electroluminescence device, owing to containing purity of color and the higher organic phosphorescent material of phosphorescence quantum yield in luminescent layer, therefore can be launched high purity blue light, and have good device performance.
This electroluminescent device due in luminescent layer, contain purity of color and phosphorescence quantum yield higher containing iridium blue phosphorescent organic electroluminescent material, it has higher effciency of energy transfer and luminous efficiency, can be widely used in the luminous fields such as blueness or white.
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. an organic phosphorescent material, is characterized in that: in described organic phosphorescent material molecule, contain bipyridine ligand, as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
2. a preparation method for organic phosphorescent material, is characterized in that, comprises the following steps:
The compd A and the compd B that provide respectively following structural formula to represent:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl;
Under anhydrous and oxygen-free condition, according to mol ratio 3:1～5:1, compd A and compd B are dissolved in the first organic solvent and are reacted, be heated to reflux and react 20～30h, after separation and purification, obtain the organic phosphorescent material as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
3. the preparation method of organic phosphorescent material as claimed in claim 2, is characterized in that, described the first organic solvent is ethylene glycol, glycerine, DMF, cellosolvo or 2-methoxyl group methyl alcohol.
4. the preparation method of organic phosphorescent material as claimed in claim 2, is characterized in that, the concentration of described compd B in the first organic solvent is 0.01～0.1mol/L.
5. the preparation method of organic phosphorescent material as claimed in claim 2, is characterized in that, described compd A can make by the following method:
The Compound C and the Compound D that provide respectively following structural formula to represent:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are all Cl, or X is that Cl and Y are F, or X is that F and Y are Cl;
In nitrogen or atmosphere of inert gases, according to mol ratio 1:1～1:2, Compound C and Compound D are dissolved in the second organic solvent, add again catalyzer and alkali, be heated to reflux and carry out Suzuki linked reaction 24～30h, after separation and purification, obtain the compd A shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
6. the preparation method of organic phosphorescent material as claimed in claim 5, is characterized in that, described the second organic solvent is toluene, DMF, Isosorbide-5-Nitrae-dioxane or dimethylbenzene.
7. the preparation method of organic phosphorescent material as claimed in claim 5, is characterized in that, the concentration of described Compound C in the second organic solvent is 0.1～0.2mol/L.
8. the preparation method of organic phosphorescent material as claimed in claim 5, is characterized in that, described catalyzer is tetra-triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, and the mole dosage of described catalyzer is 1%～5% of Compound C mole dosage.
9. the preparation method of organic phosphorescent material as claimed in claim 5, is characterized in that, described alkali be in wet chemical and the barium hydroxide octahydrate aqueous solution one or both, the mole dosage of described alkali is 2～5 times of Compound C mole dosage.
10. an organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that, and the organic phosphorescent material as claimed in claim 1 that adulterated in described luminescent layer, as shown in following structural formula:
In formula, R is amino, dimethylamino or diphenyl amino; X and Y are respectively Cl or F, or X and Y are all Cl.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010019782A1 (en) * | 1999-12-27 | 2001-09-06 | Tatsuya Igarashi | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
| CN101146814A (en) * | 2005-03-01 | 2008-03-19 | 新加坡科技研究局 | Solution processed organometallic complexes and their use in electroluminescent devices |
| CN101611045A (en) * | 2006-12-27 | 2009-12-23 | 住友化学株式会社 | Metal complexes, macromolecular compound and contain their device |
| CN102807857A (en) * | 2011-06-01 | 2012-12-05 | 海洋王照明科技股份有限公司 | Iridium-containing organic electroluminescent material and preparation method thereof and organic electroluminescent device |
-
2013
- 2013-03-20 CN CN201310091313.8A patent/CN104059628A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010019782A1 (en) * | 1999-12-27 | 2001-09-06 | Tatsuya Igarashi | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
| CN101146814A (en) * | 2005-03-01 | 2008-03-19 | 新加坡科技研究局 | Solution processed organometallic complexes and their use in electroluminescent devices |
| CN101611045A (en) * | 2006-12-27 | 2009-12-23 | 住友化学株式会社 | Metal complexes, macromolecular compound and contain their device |
| CN102807857A (en) * | 2011-06-01 | 2012-12-05 | 海洋王照明科技股份有限公司 | Iridium-containing organic electroluminescent material and preparation method thereof and organic electroluminescent device |
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| SEOK JONG LEE等: "Blue Phosphorescent Ir(III) Complex with High Color Purity: fac-Tris(2′,6′-difluoro-2,3′-bipyridinato-N,C4′)iridium(III)", 《INORGANIC CHEMISTRY》 * |
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