CN104119399A - Blue organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device - Google Patents

Blue organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device Download PDF

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CN104119399A
CN104119399A CN201310157349.1A CN201310157349A CN104119399A CN 104119399 A CN104119399 A CN 104119399A CN 201310157349 A CN201310157349 A CN 201310157349A CN 104119399 A CN104119399 A CN 104119399A
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metal complexes
blue light
iridium metal
electroluminescent materials
iridium
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周明杰
王平
张娟娟
冯小明
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention discloses a blue organic electrophosphorescent material iridium metal complex, a preparation method thereof and an organic electroluminescent device. A structural general formula of the material is shown in the specification, wherein R is a hydrogen atom, C1-C4 linear or branched alkyl or C1-C4 linear or branched alkoxy. The blue organic electrophosphorescent material iridium metal complex provided by the invention has the beneficial effects that the blue organic electrophosphorescent material iridium metal complex takes 3-(2',6'-difluoropyridine-4'-yl)pyridazine or a derivative thereof as a cyclic metal ligand; the satisfactory energy transfer efficiency and blue light emitting wavelength can be obtained and certain steric hindrance effects can be generated by introducing alkyl and alkoxy, thus reducing direction actions among metal atoms and reducing the self-quenching phenomenon of triplet excitons; meanwhile, substitution of two F-based strong electron-withdrawing groups on a stiffening pyridine ring can not only effectively perform blue shift on the light emitting wavelength but also improve the light emitting properties, thereby being beneficial for evaporation and improving the film-forming properties and the device stability.

Description

Iridium metal complexes of blue light organic phosphorescent electroluminescent materials and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to electroluminescent organic material, relate in particular to a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq 3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, make low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
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 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.Report that at present maximum, the best blue light organic phosphorescent electroluminescent materials of over-all properties is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), although people have carried out various optimization to FIrpic class OLED structure, device performance is also greatly improved, but the weakness of FIrpic maximum is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED device of making is (0.13～0.17,0.29～0.39) between, change, between this and standard blue light CIE (0.137,0.084), there is very large gap.Therefore the blue phosphorescent organic electroluminescent material of, developing high color purity becomes a megatrend of expanding blue light material research field.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
A kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, its general structure is as follows:
Wherein, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
A preparation method for iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
(1), under protection of inert gas, by structural formula be compd A and structural formula be compd B be dissolved in the first organic solvent that contains catalyzer and alkali, at 80～100 DEG C of temperature, carry out subsequently Suzuki linked reaction 4～5h, after question response stops, separating-purifying reaction solution, obtains structural formula and is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1～1:2;
(2), under protection of inert gas, described cyclic metal complexes and three is closed to acetyl acetone iridium (Ir (acac) 3) be dissolved in the second organic solvent taking mol ratio as 1:0.25～1:0.3, be heated to reflux and carry out ligand exchange reaction 25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is iridium metal complexes of blue light organic phosphorescent electroluminescent materials;
In above-mentioned formula, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
Preferably, described the first organic solvent is toluene or dimethyl formamide (DMF), and the consumption of organic solvent is enough, so that each reactants dissolved fully reaction.
Preferably, described alkali is sodium carbonate (Na 2cO 3) or salt of wormwood (K 2cO 3), the mol ratio of alkali and compd A is 2:1～5:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh 3) 4) or two (triphenyl phosphorus) dichloro close palladium (Pd (PPh 3) 2cl 2), the mol ratio of described catalyzer and compd A is 0.01:1～0.015:1.
More preferably, add Tetrabutyl amonium bromide as phase-transfer catalyst, the mol ratio of described Tetrabutyl amonium bromide and compd A consumption is 1:2.
Preferably, described the second organic solvent is glycerine, cellosolvo or propylene glycol, and the consumption of organic solvent is enough, so that each reactants dissolved fully reaction.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
Stop being chilled to after room temperature until step (1) reaction, by step (1) dichloromethane extraction, separatory for reaction product, be washed to neutrality, anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtains described cyclic metal complexes.
Preferably, the separating-purifying of described compound iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Stop being chilled to after room temperature until step (2) reaction, in step (2) reaction product, add 1N HCl, filter to obtain crude product, use successively a small amount of normal hexane, the ultrasonic lower washing of ether, then carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
A kind of organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer is the mixture of material of main part and guest materials, and wherein guest materials is the iridium metal complexes of blue light organic phosphorescent electroluminescent materials shown in following structural formula:
Wherein, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
Preferably, the doping massfraction of described guest materials in material of main part is 5%～20%.
More preferably, the doping massfraction of described guest materials in material of main part is 7%.
In the luminescent layer of organic electroluminescence device of the present invention, contain above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex, the organic electroluminescence device making can be launched high purity blue light, and has the advantages such as luminous efficiency is high, good stability.
Iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention, with 3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine or derivatives thereof is cyclic metal complexes, the introducing of alkyl, alkoxyl group can obtain satisfied energy transmission efficiency and blue light emitting wavelength, and can produce certain space steric effect, thereby the direct effect between minimizing atoms metal, the self-quenching phenomenon of minimizing triplet exciton; Meanwhile, two F base strong electron-withdrawing groups on rigidity pyridine ring replace blue shift emission wavelength effectively, can also improve luminescent properties, are beneficial to evaporation, increase film-forming properties and improve the stability of device.
Brief description of the drawings
Fig. 1 is the utilizing emitted light spectrogram of the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that makes in embodiment 1;
Fig. 2 is the structural representation of the organic electroluminescence device that makes in embodiment 8.
Embodiment
The invention reside in and select with 3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine or derivatives thereof is cyclic metal complexes, the introducing of alkyl, alkoxyl group can obtain satisfied energy transmission efficiency and blue light emitting wavelength, and can produce certain space steric effect.
The general structure of iridium metal complexes of blue light organic phosphorescent electroluminescent materials of the present invention is as follows:
In formula, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
Iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention, with 3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine or derivatives thereof is cyclic metal complexes, the introducing of alkyl, alkoxyl group can obtain satisfied energy transmission efficiency and blue light emitting wavelength, and can produce certain space steric effect, thereby the direct effect between minimizing atoms metal, the self-quenching phenomenon of minimizing triplet exciton; Meanwhile, two F base strong electron-withdrawing groups on rigidity pyridine ring replace blue shift emission wavelength effectively, can also improve luminescent properties, are beneficial to evaporation, increase film-forming properties and improve the stability of device.
The preparation method of above-mentioned iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
(1), under rare gas element (at least one in nitrogen, argon gas, lower same) protection, by structural formula be compd A and structural formula be compd B be dissolved in the first organic solvent that contains catalyzer and alkali, the Suzuki linked reaction 4～5h that refluxes at 80～100 DEG C of temperature subsequently, after question response stops, separating-purifying reaction solution, obtains structural formula and is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1～1:2; Reaction formula is as follows:
In formula, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
(2) under protection of inert gas, described cyclic metal complexes and three is closed to acetyl acetone iridium and be dissolved in the second organic solvent taking mol ratio as 1:0.25～1:0.3, be heated to reflux and carry out ligand exchange reaction 25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is iridium metal complexes of blue light organic phosphorescent electroluminescent materials; Reaction formula is:
In formula, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
Preferably, described the first organic solvent is toluene or dimethyl formamide (DMF).
Preferably, described alkali is sodium carbonate (Na 2cO 3) or salt of wormwood (K 2cO 3), the mol ratio of described alkali and compd A is 2:1～5:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium or two (triphenyl phosphorus) dichloro closes palladium, and the mol ratio of described catalyzer and compd A is 0.01:1～0.015:1.
More preferably, add Tetrabutyl amonium bromide as phase-transfer catalyst, the mol ratio of described Tetrabutyl amonium bromide and compd A consumption is 1:2.
Preferably, described the second organic solvent is glycerine, cellosolvo or propylene glycol.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
Stop being chilled to after room temperature until step (1) reaction, by step (1) dichloromethane extraction, separatory for reaction product, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtains described cyclic metal complexes.
Preferably, the separating-purifying of described compound iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Stop being chilled to after room temperature until step (2) reaction, in step (2), add 1N HCl, filter to obtain crude product, use successively a small amount of normal hexane, the ultrasonic lower washing of ether, then carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
In addition, be also necessary to provide a kind of blue light organic phosphorescent electroluminescent materials metal iridium complex organic electroluminescence device.
A kind of organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer is the mixture of material of main part and guest materials, and wherein guest materials is the iridium metal complexes of blue light organic phosphorescent electroluminescent materials shown in following structural formula:
Wherein, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
Preferably, the doping massfraction of described guest materials in material of main part is 5%～20%.
More preferably, the doping massfraction of described guest materials in material of main part is 7%.
In the luminescent layer of organic electroluminescence device of the present invention, contain above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex, the organic electroluminescence device making can be launched high purity blue light, and has the advantages such as luminous efficiency is high, good stability.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine is synthetic
Under nitrogen protection; in reactor, add 3.18g (20mmol) 3-bromine pyridazine (A1), 3.81g (24mmol) 2; 6-difluoro pyridine-4-boric acid (B), 80mL toluene, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 5.53g (40mmol) Anhydrous potassium carbonate, 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium, then at 100 DEG C of stirring and refluxing 4h.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.43g, yield is 62.9%.
Structural Identification:
Mass spectrum (MS m/z): 193.0 (M +)
Ultimate analysis: C 9h 5f 2n 3
Theoretical value: C, 55.96; H, 2.61; F, 19.67; N, 21.75;
Measured value: C, 55.93; H, 2.64; F, 19.65; N, 21.77.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; by 1.93g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl) pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL glycerine, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.39g, and yield is 20.3%.
Structural Identification:
Mass spectrum (MS m/z): 769.1 (M +)
Ultimate analysis: C 27h 12f 6irN 9
Theoretical value: C, 42.19; H, 1.57; F, 14.83; Ir, 25.01; N, 16.40;
Measured value: C, 42.17; H, 1.59; F, 14.80; Ir, 25.02; N, 16.42.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine-N, C 2') close iridium.
Fig. 1 is the utilizing emitted light spectrogram of the blue light organic phosphorescent electroluminescent materials metal iridium complex that makes of the embodiment of the present invention one.As shown in Figure 1, transverse axis is wavelength (Wavelength, the nm of unit), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), and end product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 452nm place, has an acromion at 482nm place simultaneously, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, 10 -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.15, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine is synthetic
Under nitrogen protection; in reactor, add 3.46g (20mmol) 3-bromo-6-methyl pyridazine (A2), 3.18g (20mmol) B, 80mL DMF, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 10.6g (100mmol) anhydrous sodium carbonate, 0.23g (0.2mmol) four (triphenyl phosphorus) to close palladium, then stirring and refluxing 4h at 100 DEG C.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.48g, yield is 59.8%.
Structural Identification:
Mass spectrum (MS m/z): 207.1 (M +)
Ultimate analysis: C 10h 7f 2n 3
Theoretical value: C, 57.97; H, 3.41; F, 18.34; N, 20.28;
Measured value: C, 57.92; H, 3.45; F, 18.32; N, 20.31.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; by 2.07g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL2-ethoxy ethanol, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.36g, and yield is 17.8%.
Structural Identification:
Mass spectrum (MS m/z): 811.1 (M +)
Ultimate analysis: C 30h 18f 6irN 9
Theoretical value: C, 44.44; H, 2.24; F, 14.06; Ir, 23.71; N, 15.55;
Measured value: C, 44.41; H, 2.25; F, 14.08; Ir, 23.74; N, 15.52.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methyl pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 458nm place, has an acromion, 10 at 488nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.10.
Embodiment 3: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine is synthetic
Under nitrogen protection; in reactor, add 3.74g (20mmol) 3-bromo-6-ethyl pyridazine (A3), 6.36g (40mmol) B, 80mL DMF, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 6.36g (60mmol) anhydrous sodium carbonate, 0.23g (0.2mmol) four (triphenyl phosphorus) to close palladium, at 80 DEG C of stirring and refluxing 5h.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.39g, yield is 54.0%.
Structural Identification:
Mass spectrum (MS m/z): 221.1 (M +)
Ultimate analysis: C 11h 9f 2n 3
Theoretical value: C, 59.73; H, 4.10; F, 17.18; N, 19.00;
Measured value: C, 59.70; H, 4.12; F, 17.15; N, 19.04.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; 2.21g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL glycerine, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.34g, and yield is 15.9%.
Structural Identification:
Mass spectrum (MS m/z): 853.2 (M +)
Ultimate analysis: C 33h 24f 6irN 9
Theoretical value: C, 46.48; H, 2.84; F, 13.37; Ir, 22.54; N, 14.78;
Measured value: C, 46.45; H, 2.85; F, 13.35; Ir, 22.57; N, 14.79.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-ethyl pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 458nm place, has an acromion, 10 at 487nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.08.
Embodiment 4: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine is synthetic
Under nitrogen protection; in reactor, add 4.30g (20mmol) 3-bromo-6-tertiary butyl pyridazine (A4), 3.81g (24mmol) B, 80mL DMF, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 5.53g (40mmol) Anhydrous potassium carbonate, 0.14g (0.2mmol) two (triphenyl phosphorus) dichloro to close palladium, stirring and refluxing 5h at 95 DEG C.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.49g, yield is 49.9%.
Structural Identification:
Mass spectrum (MS m/z): 249.1 (M +)
Ultimate analysis: C 13h 13f 2n 3
Theoretical value: C, 62.64; H, 5.26; F, 15.24; N, 16.86;
Measured value: C, 62.60; H, 5.25; F, 15.27; N, 16.90.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; by 3.16g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL propylene glycol, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.33g, and yield is 14.1%.
Structural Identification:
Mass spectrum (MS m/z): 937.3 (M +)
Ultimate analysis: C 39h 36f 6irN 9
Theoretical value: C, 49.99; H, 3.87; F, 12.17; Ir, 20.51; N, 13.45;
Measured value: C, 49.95; H, 3.85; F, 12.20; Ir, 20.52; N, 13.47.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-tertiary butyl pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 458nm place, has an acromion, 10 at 488nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.07.
Embodiment 5: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine is synthetic
Under argon shield; in reactor, add 3.78g (20mmol) 3-bromo-6-methoxyl group pyridazine (A5), 3.81g (24mmol) B, 80mL DMF, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 4.24g (40mmol) Anhydrous potassium carbonate, 0.21g (0.3mmol) bi triphenyl phosphorus dichloro to close palladium, at 100 DEG C of stirring and refluxing 4h.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.59g, yield is 58.0%.
Structural Identification:
Mass spectrum (MS m/z): 223.1 (M +)
Ultimate analysis: C 10h 7f 2n 3o
Theoretical value: C, 53.82; H, 3.16; F, 17.03; N, 18.83; O, 7.17;
Measured value: C, 53.78; H, 3.15; F, 17.05; N, 18.86; O, 7.18.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine-N, C 2') close synthesizing of iridium
Under argon shield; by 2.90g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL glycerine, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.41g, and yield is 15.9%.
Structural Identification:
Mass spectrum (MS m/z): 859.1 (M +)
Ultimate analysis: C 30h 18f 6irN 9o 3
Theoretical value: C, 41.96; H, 2.11; F, 13.27; Ir, 22.38; N, 14.68; O, 5.59;
Measured value: C, 41.95; H, 2.10; F, 13.29; Ir, 22.35; N, 14.69; O, 5.61.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-methoxyl group pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 459nm place, has an acromion, 10 at 488nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.08.
Embodiment 6: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine is synthetic
Under nitrogen protection; in reactor, add 4.06g (20mmol) 3-bromo-6-oxyethyl group pyridazine (A6), 3.81g (24mmol) B, 80mL DMF, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 5.53g (40mmol) Anhydrous potassium carbonate, 0.23g (0.2mmol) four (triphenyl phosphorus) to close palladium, at 85 DEG C of stirring and refluxing 4h.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.61g, yield is 55.0%.
Structural Identification:
Mass spectrum (MS m/z): 237.1 (M +)
Ultimate analysis: C 11h 9f 2n 3o
Theoretical value: C, 55.70; H, 3.82; F, 16.02; N, 17.71; O, 6.74;
Measured value: C, 55.65; H, 3.80; F, 16.06; N, 17.72; O, 6.76.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; by 2.37g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine and 1.22g (2.5mmol) three close acetyl acetone iridium and be dissolved in 50mL propylene glycol, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.31g, and yield is 13.8%.
Structural Identification:
Mass spectrum (MS m/z): 901.1 (M +)
Ultimate analysis: C 33h 24f 6irN 9o 3
Theoretical value: C, 44.00; H, 2.69; F, 12.65; Ir, 21.34; N, 13.99; O, 5.33;
Measured value: C, 44.03; H, 2.66; F, 12.62; Ir, 21.36; N, 13.97; O, 5.36.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-oxyethyl group pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 459nm place, has an acromion, 10 at 488nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.06.
Embodiment 7: title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine-N, C 2') close synthesizing of iridium
(1) 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine is synthetic
Under nitrogen protection; in reactor, add 4.62g (20mmol) 3-bromo-6-butoxy pyridazine (A7), 3.81g (24mmol) B, 80mL toluene, 20mL water, 3.22g (10mmol) Tetrabutyl amonium bromide, 4.24g (40mmol) anhydrous sodium carbonate, 0.21g (0.3mmol) two (triphenyl phosphorus) dichloro to close palladium, at 90 DEG C of stirring and refluxing 4h.Question response liquid cooling is to room temperature, and dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtain solid 2.55g, yield is 48.1%.
Structural Identification:
Mass spectrum (MS m/z): 265.1 (M +)
Ultimate analysis: C 13h 13f 2n 3o
Theoretical value: C, 58.86; H, 4.94; F, 14.32; N, 15.84; O, 6.03;
Measured value: C, 58.82; H, 4.93; F, 14.35; N, 15.85; O, 6.04.
The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine.
(2) title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine-N, C 2') close synthesizing of iridium
Under nitrogen protection; by 2.65g (10mmol) 3-(2 '; 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine and 1.47g (3mmol) three close acetyl acetone iridium and be dissolved in 50mL2-ethoxy ethanol, is heated to reflux state, stirring reaction 25h.Naturally be chilled to after room temperature, add appropriate 1N HCl, filter to obtain crude product.Use successively a small amount of normal hexane, the ultrasonic lower washing of ether.Carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains final title complex 0.38g, and yield is 12.8%.
Structural Identification:
Mass spectrum (MS m/z): 985.2 (M +)
Ultimate analysis: C 39h 36f 6irN 9o 3
Theoretical value: C, 47.56; H, 3.68; F, 11.57; Ir, 19.52; N, 12.80; O, 4.87;
Measured value: C, 47.51; H, 3.65; F, 11.60; Ir, 19.53; N, 12.83; O, 4.88.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl)-6-butoxy pyridazine-N, C 2') close iridium.
End product is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 460nm place, has an acromion, 10 at 490nm place simultaneously -5the CH of M end product 2cl 2solution is at 298K temperature, with the H of 0.1N sulfuric acid Kui Lin 2sO 4solution is standard Φ pL=0.54, record the Φ of end product pL=0.08.
Embodiment 8
The present embodiment is organic electroluminescence device, and the title complex three (3-(2 ', 6 '-difluoro pyridine-4 '-yl) pyridazine-N, C2 ') that it makes with embodiment 1 closes iridium (representing using M1) as luminescent layer doping guest materials; As shown in Figure 2, the structure of organic electroluminescence device comprises the transparent anode 301, hole injection layer 302, hole transmission layer 303, electronic barrier layer 304, luminescent layer 305, hole blocking layer 306, electron transfer layer 307, electronic injection buffer layer 308, the negative electrode 309 that stack gradually.
The preparation technology of this organic electroluminescence device:
On a glass-based plate, depositing a layer thickness is 200nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/ is as transparent anode 301, on anode 301, prepare successively by vacuum evaporation the m-MTDATA(4 that a layer thickness is 40nm, 4 ', 4 ' '-tri-(N-3-aminomethyl phenyl-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, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electronic blocking material is as electronic barrier layer 304, a layer thickness is that the mCP mixing and doping material that is 7%M1 doped with massfraction of 30nm is as luminescent layer 305, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 305 again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 306, thickness is that the Alq3 (three (oxine) aluminium) of 35nm is as electron transfer layer 307, thickness is that the LiF of 1nm is as electronic injection buffer layer 308, finally on buffer layer, adopt the metal A l that vacuum plating techniques of deposition thickness is 120nm, as the negative electrode 309 of device.Therefore, the structure of this organic electroluminescence device can be also ITO/m-MTDATA/NPB/mCP/mCP:M1/BCP/Alq3/LiF/Al; Wherein, mCP:M1 represents that M1 is doped in mCP, and slash "/" represents laminate structure.
Know through performance test, the maximum emission wavelength of the volume electroluminescent spectrum of this device is positioned at 460nm, has an acromion at 490nm place, and maximum lumen efficiency is 16.2lm/W, and maximum external quantum efficiency is 10.1%.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. an iridium metal complexes of blue light organic phosphorescent electroluminescent materials, is characterized in that, general structure is as follows:
Wherein, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
2. a preparation method for iridium metal complexes of blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:
(1), under protection of inert gas, by structural formula be compd A and structural formula be compd B be dissolved in the first organic solvent that contains catalyzer and alkali, at 80～100 DEG C of temperature, carry out subsequently Suzuki linked reaction 4～5h, after question response stops, separating-purifying reaction solution, obtains structural formula and is cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1～1:2;
(2) under protection of inert gas, described cyclic metal complexes and three is closed to acetyl acetone iridium and be dissolved in the second organic solvent taking mol ratio as 1:0.25～1:0.3, be heated to reflux and carry out ligand exchange reaction 25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is iridium metal complexes of blue light organic phosphorescent electroluminescent materials;
In above-mentioned formula, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
3. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described the first organic solvent is toluene or dimethyl formamide.
4. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described alkali is sodium carbonate or salt of wormwood, and the mol ratio of described alkali and compd A is 2:1～5:1.
5. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, it is characterized in that, described catalyzer is that four (triphenylphosphines) close palladium or two (triphenyl phosphorus) dichloro closes palladium, and the mol ratio of described catalyzer and compd A is 0.01:1～0.015:1.
6. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 5, is characterized in that, adds Tetrabutyl amonium bromide as phase-transfer catalyst, and the mol ratio of described Tetrabutyl amonium bromide and compd A consumption is 1:2.
7. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described the second organic solvent is for being glycerine, cellosolvo or propylene glycol.
8. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described cyclic metal complexes comprises:
Stop being chilled to after room temperature until step (1) reaction, by step (1) dichloromethane extraction, separatory product for, be washed to neutrality, use anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant, after being dried, obtains described cyclic metal complexes.
9. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described compound iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Stop being chilled to after room temperature until step (2) reaction, in step (2) reaction product, add 1N hydrochloric acid, filter to obtain crude product, use successively a small amount of normal hexane, the ultrasonic lower washing of ether, then carry out silica gel column chromatography separation taking methylene dichloride as elutriant, steaming desolventizes, and after being dried, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, the material of described luminescent layer is the mixture of material of main part and guest materials, and wherein guest materials is the iridium metal complexes of blue light organic phosphorescent electroluminescent materials shown in following structural formula:
Wherein, R is hydrogen atom, C 1～C 4straight or branched alkyl, or C 1～C 4straight or branched alkoxyl group.
CN201310157349.1A 2013-04-28 2013-04-28 Blue organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device Pending CN104119399A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1664054A (en) * 2004-02-02 2005-09-07 三星Sdi株式会社 IR compound and organic electroluminescent device using the same
CN102140119A (en) * 2010-12-13 2011-08-03 南京邮电大学 Phosphorescent iridium complex and electroluminescence device thereof
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1664054A (en) * 2004-02-02 2005-09-07 三星Sdi株式会社 IR compound and organic electroluminescent device using the same
CN102140119A (en) * 2010-12-13 2011-08-03 南京邮电大学 Phosphorescent iridium complex and electroluminescence device thereof
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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Application publication date: 20141029