CN104177411A - Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device - Google Patents
Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device Download PDFInfo
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- CN104177411A CN104177411A CN201310192103.8A CN201310192103A CN104177411A CN 104177411 A CN104177411 A CN 104177411A CN 201310192103 A CN201310192103 A CN 201310192103A CN 104177411 A CN104177411 A CN 104177411A
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Abstract
The invention discloses a blue electrophosphorescent material iridium metal complex, its preparation method and an organic electroluminescent device. The general structural formula of the material is as defined in the specification, wherein R is a hydrogen atom or C1-C20 alkyl group. According to the blue electrophosphorescent material iridium metal complex, 2-(2',6'-di(trifluoromethyl)pyridine-3'-yl)pyrimidine is used as a cyclometallated ligand and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is used as an auxiliary ligand so as to synthesize a blue electrophosphorescent material iridium metal complex; and by chemical modification of introducing an alkyl chain to a pyrimidine ring of the cyclometallated ligand, emitting color of the material is adjusted so as to obtain bluer phosphorescence emission with long emission wavelength.
Description
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, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened 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, in building-up process, reaction conditions is gentle, 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.
An iridium metal complexes of blue light organic phosphorescent electroluminescent materials, general structure is as follows:
Wherein, R is hydrogen atom or C
1～C
20alkyl.
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, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 8～15h at 85～100 ℃ of temperature, 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; R is hydrogen atom or C
1～C
20alkyl;
(2) under protection of inert gas, described cyclic metal complexes and three hydration iridous chlorides be take to mol ratio as 2:1～3:1 is dissolved in the mixed solvent of cellosolvo and water formation, heat mixed solvent to reflux state stirring reaction 22～25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
chlorine bridge dipolymer; R is hydrogen atom or C
1～C
20alkyl;
(3), under protection of inert gas, by described chlorine bridge dipolymer and structural formula, be
compound C take in the second organic solvent that mol ratio contains sodium methylate or sodium ethylate as 1:2～1:3 is dissolved in, obtain mixing solutions, heating mixing solutions to 40～84 ℃, stirring reaction 10～20h, is cooled to room temperature, separating-purifying obtains structural formula and is
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; R is hydrogen atom or C
1～C
20alkyl.
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 2:1～4:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1～0.06:1.
Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1～0.2mol/L.
Preferably, the volumetric molar concentration of described three hydration iridous chlorides in the mixed solvent of cellosolvo and water formation is 0.04～0.05mol/L.
Preferably, the volume ratio of described cellosolvo and water is 3:1.
Preferably, described the second organic solvent is 1,2-ethylene dichloride, trichloromethane or methylene dichloride.
Preferably, the mol ratio of described sodium methylate or sodium ethylate and described chlorine bridge dipolymer is 8:1～12:1.
Preferably, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01～0.02mol/L.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
Question response stops being chilled to after room temperature, and dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution that sherwood oil and methylene dichloride or ethylene dichloride form of take is separated as elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after dry.
More preferably, the volume ratio of described sherwood oil and methylene dichloride or ethylene dichloride is 1:5～1:8.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:
Question response stops being chilled to after room temperature, rotates and steams except partial solvent, adds appropriate distilled water, filters and obtains solid, and solid is used distilled water, methanol wash successively, after being dried, obtains described chlorine bridge dipolymer.
Preferably, the separating-purifying of described iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Question response stops being chilled to after room temperature, concentrated remove portion solvent, and the appropriate distilled water of impouring, has solid to separate out; Filter and collect crude product, crude product is used deionized water, methanol wash for several times successively, after the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol formation, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
Blue light organic phosphorescent electroluminescent materials metal iridium complex provided by the invention is with 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand.For electrical pyrimidine ring, be conducive to improve the lumo energy of material, the pyridine ring of short of electricity and encircle the HOMO energy level that two strong electron-withdrawing substituent trifluoromethyls are conducive to reduce material, makes the emission wavelength of material obtain effective blue shift; The difference of the straight or branched type alkyl of different lengths being introduced to pyrimidine ring replaces position, can not only increase the solvability of material in ordinary organic solvents, the space steric effect that it produces on pyrimidine ring can also reduce the interaction force between material molecule, to reduce the self-quenching phenomenon of triplet exciton in solid film, thereby obtain satisfied luminous efficiency; Simultaneously, on phenyl ring 4, two strong electron-withdrawing groups of 6-position are rolled into a ball trifluoromethyl and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1,2, the introducing of 4-triazole is except making emission wavelength blue shift, different luminescent properties of joining type title complex can also can reduce evaporation temperature because intramolecular energy shifts be improved and improve, and increases film-forming type and improves the stability of device.
An organic electroluminescence device, comprises luminescent layer, the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that adulterates in described luminescent layer, and general structure is as follows:
Wherein, R is hydrogen atom or C
1～C
20alkyl.
In the luminescent layer of organic electroluminescence device of the present invention, contain above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention, owing to containing the organic electromechanical phosphorescent material metal iridium complex of launching blue light wavelength in luminescent layer, can be launched high purity blue light and good device performance thereby it has advantages of.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the iridium metal complexes of blue light organic phosphorescent electroluminescent materials of an embodiment;
Fig. 2 is the utilizing emitted light spectrogram of the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that makes in embodiment 1;
Fig. 3 is the structural representation of the organic electroluminescence device that makes in Application Example.
Embodiment
The invention reside in and select with 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine or derivatives thereof is cyclic metal complexes, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand, synthetic a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and by realizing the adjusting to material glow color to introducing the chemically modified of alkyl chain on the pyrimidine ring of cyclic metal complexes, thereby the more blue phosphorescent emissions of emission wavelength obtained.The object of the present invention is to provide a kind of like this blue light organic phosphorescent material iridium metal complex and preparation and organic electroluminescence device.
The general structure of iridium metal complexes of blue light organic phosphorescent electroluminescent materials of the present invention is as follows:
Wherein, R is hydrogen atom or C
1～C
20alkyl, the structural formula of described cyclic metal complexes is:
Refer to Fig. 1, the preparation method of above-mentioned iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
Under S1, 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, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 8～15h at 85～100 ℃ of temperature, 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; R is hydrogen atom or C
1～C
20alkyl, reaction formula is:
Under S2, protection of inert gas, described cyclic metal complexes and three hydration iridous chlorides be take to mol ratio as 2:1～3:1 is dissolved in the mixed solvent of cellosolvo and water, heat mixed solvent to reflux state stirring reaction 22～25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
chlorine bridge dipolymer; R is hydrogen atom or C
1～C
20alkyl, reaction formula is:
Under S3, protection of inert gas, by described chlorine bridge dipolymer and structural formula, be
compound C take in the second organic solvent that mol ratio contains sodium methylate or sodium ethylate as 1:2～1:3 is dissolved in, obtain mixing solutions, heating mixing solutions to 40～84 ℃, stirring reaction 10～20h, is cooled to room temperature, separating-purifying obtains structural formula and is
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; R is hydrogen atom or C
1～C
20alkyl, reaction formula is:
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 2:1～4:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1～0.06:1.
Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1～0.2mol/L.
Preferably, the volumetric molar concentration of described three hydration iridous chlorides in the mixed solvent of cellosolvo and water formation is 0.04～0.05mol/L.
Preferably, the volume ratio of described cellosolvo and water is 3:1.
Preferably, described the second organic solvent is 1,2-ethylene dichloride, trichloromethane or methylene dichloride.
Preferably, the mol ratio of described sodium methylate or sodium ethylate and described chlorine bridge dipolymer is 8:1～12:1.
Preferably, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01～0.02mol/L.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
Question response stops being chilled to after room temperature, and dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution that sherwood oil and methylene dichloride or ethylene dichloride form of take is separated as elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after dry.
More preferably, the volume ratio of described sherwood oil and methylene dichloride or ethylene dichloride is 1:5～1:8.
Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:
Question response stops being chilled to after room temperature, rotates and steams except partial solvent, adds appropriate distilled water, filters and obtains solid, and solid is used distilled water, methanol wash successively, after being dried, obtains described chlorine bridge dipolymer.
Preferably, the separating-purifying of described iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Question response stops being chilled to after room temperature, concentrated remove portion solvent, and the appropriate distilled water of impouring, has solid to separate out; Filter and collect crude product, crude product is used deionized water, methanol wash for several times successively, after the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol formation, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
Blue light organic phosphorescent electroluminescent materials metal iridium complex provided by the invention is with 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand.For electrical pyrimidine ring, be conducive to improve the lumo energy of material, the pyridine ring of short of electricity and encircle the HOMO energy level that two strong electron-withdrawing substituent trifluoromethyls are conducive to reduce material, makes the emission wavelength of material obtain effective blue shift; The difference of the straight or branched type alkyl of different lengths being introduced to pyrimidine ring replaces position, can not only increase the solvability of material in ordinary organic solvents, the space steric effect that it produces on pyrimidine ring can also reduce the interaction force between material molecule, to reduce the self-quenching phenomenon of triplet exciton in solid film, thereby obtain satisfied luminous efficiency; Simultaneously, on phenyl ring 4, two strong electron-withdrawing groups of 6-position are rolled into a ball trifluoromethyl and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1,2, the introducing of 4-triazole is except making emission wavelength blue shift, different luminescent properties of joining type title complex can also can reduce evaporation temperature because intramolecular energy shifts be improved and improve, and increases film-forming type and improves the stability of device.
In addition, be also necessary to provide a kind of blue light organic phosphorescent electroluminescent materials metal iridium complex organic electroluminescence device.
An organic electroluminescence device, comprises luminescent layer, the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that adulterates in described luminescent layer, and general structure is as follows:
Wherein, R is hydrogen atom or C
1～C
20alkyl.
In the luminescent layer of organic electroluminescence device of the present invention, contain above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention, owing to containing the organic electromechanical phosphorescent material metal iridium complex of launching blue light wavelength in luminescent layer, can be launched high purity blue light and good device performance thereby it has advantages of.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
(1) 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine is synthetic
Under nitrogen protection; by 0.80g (5mmol) 2-bromo pyrimi piperidine (A1), 1.55g (6mmol) 2; 6-bis-(trifluoromethyl) pyridine-3-boric acid (B) and 0.35g (0.3mmol) four (triphenyl phosphorus) close palladium and are dissolved in 15mL toluene, then drip 10mL containing the aqueous solution formation reaction solution of 1.66g (12mmol) salt of wormwood.Reacting by heating liquid, stirring reaction 8h under 100 ℃ of state of temperatures.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.The mixed solution that sherwood oil and dichloro hexane form as 1:6 by volume of take is separated as elutriant carries out silica gel column chromatography, after dry solid 0.66g, yield is 45.0%.
Structural Identification:
Mass spectrum (MS m/z): 293.0 (M
+)
Ultimate analysis: C
11h
5f
6n
3
Theoretical value: C, 45.07; H, 1.72; F, 38.88; N, 14.33;
Measured value: C, 45.12; H, 1.66; F, 38.93; N, 14.29.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine
Under nitrogen protection, by 0.36g (1mmol) three hydration iridous chloride (IrCl
33H
2o) and 0.73g (2.5mmol) 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine is dissolved in the mixed solvent that cellosolvo that 25mL volume ratio is 3:1 and water forms, and heating mixed solvent is to stirring reaction 24h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.45g, and yield is 55.4%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, C of title complex
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
Under nitrogen protection; by 0.81g (0.5mmol) part, be 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine containing iridium dichloro dimer and 0.27g (1.2mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1; 2; 4-triazole (C) is dissolved in 15mL trichloromethane; drip subsequently 10mL containing the chloroform soln formation mixing solutions of 0.27g (5mmol) sodium methylate, stirring heating mixing solutions is warming up to 62 ℃ of reflux states reaction 15h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.46g pure products, and yield is 46.5%.
Structural Identification:
Mass spectrum (MS m/z): 990.1 (M
+)
Ultimate analysis: C
30h
12f
15irN
10
Theoretical value: C, 36.41; H, 1.22; F, 28.79; Ir, 19.42; N, 14.15;
Measured value: C, 36.45; H, 1.14; F, 28.85; Ir, 19.38; N, 14.18.
Fig. 2 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 1.As shown in Figure 2, 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
-6the maximum emission peak of the emmission spectrum M), at 435nm place, has an acromion at 466nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, concentration is 10
-6two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, the C of M
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the CH of iridium end product
2cl
2solution, at 298K temperature, be take concentration as～10
-6the CH of the FIrpic of M
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.35, the blue light organic phosphorescent electroluminescent materials metal iridium complex of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2: title complex two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
(1) 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine is synthetic
Under nitrogen protection; 0.86g (5mmol) the bromo-5-methylpyrimidine of 2-(A2), 1.29g (5mmol) compd B and 0.18g (0.25mmol) dichloro two (triphenyl phosphorus) are closed to palladium and be dissolved in 30mL DMF, drip 20mL containing the aqueous solution formation reaction solution of 1.59g (15mmol) sodium carbonate.Stirring reaction 10h under reacting by heating liquid to 90 ℃ state of temperature.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.The mixed solution that sherwood oil and methylene dichloride form as 1:8 by volume of take is separated as elutriant carries out silica gel column chromatography, after dry solid 0.63g, yield is 41.0%.
Structural Identification:
Mass spectrum (MS m/z): 307.1 (M
+)
Ultimate analysis: C
12h
7f
6n
3
Theoretical value: C, 46.92; H, 2.30; F, 37.11; N, 13.68;
Measured value: C, 46.95; H, 2.32; F, 37.04; N, 13.69.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine
Under nitrogen protection; by 0.36g (1mmol) three hydration iridous chlorides and 0.92g (3mmol) 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine is dissolved in the mixed solvent that cellosolvo that 25mL volume ratio is 3:1 and water forms, and heating mixed solvent is to stirring reaction 22h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.42g, and yield is 50.0%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine-N, C of title complex
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
Under nitrogen protection; by 0.84g (0.5mmol) part, be 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine is dissolved in 20mL methylene dichloride containing iridium dichloro dimer and 0.21g (1mmol) Compound C; drip subsequently 10mL containing the dichloromethane solution formation mixing solutions of 0.27g (4mmol) sodium ethylate, stirring heating mixing solutions is warming up to 40 ℃ of reflux states reaction 20h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.43g pure products, and yield is 42.2%.Structural Identification:
Mass spectrum (MS m/z): 1018.1 (M
+)
Ultimate analysis: C
32h
16f
15irN
10
Theoretical value: C, 37.76; H, 1.58; F, 28.00; Ir, 18.89; N, 13.76;
Measured value: C, 37.73; H, 1.63; F, 28.04; Ir, 18.82; N, 13.78.
Two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close iridium end product CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 433nm place, has an acromion at 463nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.10, the blue light organic phosphorescent electroluminescent materials metal iridium complex of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3: title complex two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
(1) 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine is synthetic
Under nitrogen protection; 1.08g (5mmol) 2-bromo-5-tertiary butyl pyrimidine (A3), 2.07g (8mmol) compd B and 0.17g (0.15mmol) four (triphenyl phosphorus) are closed to palladium and be dissolved in 25mL DMF, drip 10mL containing the aqueous solution formation reaction solution of 2.12g (20mmol) sodium carbonate.Stirring reaction 12h under reacting by heating liquid to 85 ℃ state.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.The mixing solutions that sherwood oil and methylene dichloride form as 1:8 by volume of take is separated as elutriant carries out silica gel column chromatography, after dry solid 0.49g, yield is 28.1%.
Structural Identification:
Mass spectrum (MS m/z): 349.1 (M
+)
Ultimate analysis: C
15h
13f
6n
3
Theoretical value: C, 51.58; H, 3.75; F, 32.64; N, 12.03;
Measured value: C, 51.63; H, 3.66; F, 32.69; N, 12.02.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine
Under nitrogen protection; by 0.36g (1mmol) three hydration iridous chlorides and 0.87g (2.5mmol) 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine is dissolved in the mixed solvent that cellosolvo that 20mL volume ratio is 3:1 and water forms, and is uniformly mixed solvent reaction 25h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.21g, and yield is 22.7%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C of title complex
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
Under nitrogen protection; by 0.74g (0.4mmol) part, be 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine is dissolved in 20mL trichloromethane containing iridium dichloro dimer and 0.21g (1mmol) Compound C; drip subsequently 10mL containing the chloroform soln formation mixing solutions of 0.33g (4.8mmol) sodium ethylate, stirring heating mixing solutions is warming up to 62 ℃ of reflux states reaction 12h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.33g pure products, and yield is 37.4%.
Structural Identification:
Mass spectrum (MS m/z): 1102.2 (M
+)
Ultimate analysis: C
38h
28f
15irN
10
Theoretical value: C, 41.42; H, 2.56; F, 25.86; Ir, 17.44; N, 12.71;
Measured value: C, 41.47; H, 2.51; F, 25.89; Ir, 17.41; N, 12.72.
Two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close iridium end product CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 439nm place, has an acromion at 470nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.20, the blue light organic phosphorescent electroluminescent materials metal iridium complex of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 4: title complex two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
(1) 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine is synthetic
Under nitrogen protection; 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine (A4), 2.59g (10mmol) compd B and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) are closed to palladium and be dissolved in 30mL toluene, in reaction system, drip 20mL containing the aqueous solution formation reaction solution of 1.38g (10mmol) salt of wormwood subsequently.Stirring reaction 15h under reacting by heating liquid to 100 ℃ state of temperature.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.The mixed solution that sherwood oil and methylene dichloride form as 1:5 by volume of take is separated as elutriant carries out silica gel column chromatography, after dry solid 0.37g, yield is 12.9%.
Structural Identification:
Mass spectrum (MS m/z): 573.3 (M
+)
Ultimate analysis: C
31h
45f
6n
3
Theoretical value: C, 64.90; H, 7.91; F, 19.87; N, 7.32;
Measured value: C, 64.94; H, 7.82; F, 19.90; N, 7.34.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine
Under nitrogen protection; by 0.18g (0.5mmol) three hydration iridous chlorides and 0.57g (1mmol) 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine is dissolved in the mixed solvent that cellosolvo that 10mL volume ratio is 3:1 and water forms, and is uniformly mixed solvent reaction 24h under reflux state.Be chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid is used distilled water, methanol wash successively, after being dried, obtains solids 0.09g, and yield is 13.1%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C of title complex
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the synthetic of iridium
Under nitrogen protection; by 0.82g (0.3mmol) part, be 2-(2'; 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine is dissolved in 20mL1 containing iridium dichloro dimer and 0.19g (0.9mmol) Compound C; in 2-ethylene dichloride; drip subsequently 10mL containing 1 of 0.16g (3mmol) sodium methylate; 2-dichloroethane solution forms mixing solutions, and stirring heating mixing solutions is warming up to 84 ℃ of reflux state reaction 10h.Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid is used deionized water, methanol wash for several times successively, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains 0.11g pure products, and yield is 11.8%.
Structural Identification:
Mass spectrum (MS m/z): 1550.7 (M
+)
Ultimate analysis: C
70h
92f
15irN
10
Theoretical value: C, 54.22; H, 5.98; F, 18.38; Ir, 12.40; N, 9.03;
Measured value: C, 54.25; H, 5.92; F, 18.43; Ir, 12.35; N, 9.05.
Two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close iridium end product CH at 298K temperature
2cl
2solution (～10
-6the maximum emission peak of the emmission spectrum M) is at 450nm place, has an acromion at 480nm place simultaneously, with the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26), record the Φ of end product
pL=0.08, the blue light organic phosphorescent electroluminescent materials metal iridium complex of visible the present embodiment has higher luminous quantum efficiency.
Application Example
The present embodiment is organic electroluminescence device, its title complex making with embodiment 1 two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close iridium (M1 of usining represents) as luminescent layer doping guest materials; Structural formula is:
As shown in Figure 3, the structure of organic electroluminescence device 300 comprises 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 stacking 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 Ω/ is as transparent anode 301, by vacuum evaporation, on anode 301, prepare successively 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 be 30nm doped with massfraction, be that the mCP mixing and doping material of 7% M1 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, negative electrode 309 as device.Therefore, the structure of this organic electroluminescence device is: 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.
By Keithley source measuring system (Keithley 2400 Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature: the maximum emission wavelength of the electroluminescent spectrum of device is positioned at 440nm, at 471nm place, there is an acromion, maximum current efficiency is 9.3cd/A, and maximum external quantum efficiency is 7.7%.
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 or C
1～C
20alkyl.
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, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 8～15h at 85～100 ℃ of temperature, after question response stops, separating-purifying reaction solution, obtains structural formula and is
cyclic metal complexes; Wherein, the mol ratio of described compd A and compd B is 1:1～1:2; Wherein, R is hydrogen atom or C
1～C
20alkyl;
(2) under protection of inert gas, described cyclic metal complexes and three hydration iridous chlorides be take to mol ratio as 2:1～3:1 is dissolved in the mixed solvent of cellosolvo and water formation, heat mixed solvent to reflux state stirring reaction 22～25h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
chlorine bridge dipolymer; Wherein, R is hydrogen atom or C
1～C
20alkyl;
(3), under protection of inert gas, by described chlorine bridge dipolymer and structural formula, be
compound C take in the second organic solvent that mol ratio contains sodium methylate or sodium ethylate as 1:2～1:3 is dissolved in, obtain mixing solutions, heating mixing solutions to 40～84 ℃, stirring reaction 10～20h, is cooled to room temperature, separating-purifying obtains structural formula and is
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom or C
1～C
20alkyl.
3. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the mol ratio of described alkali and compd A is 2:1～4:1.
4. 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 dichloro two (triphenyl phosphorus) closes palladium, and the mol ratio of described catalyzer and compd A is 0.03:1～0.06:1.
5. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the volumetric molar concentration of described compd A in reaction solution is 0.1～0.2mol/L.
6. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01～0.02mol/L.
7. 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:
Question response stops being chilled to after room temperature, and dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution that sherwood oil and methylene dichloride or ethylene dichloride form of take is separated as elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after dry.
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 chlorine bridge dipolymer comprises:
Question response stops being chilled to after room temperature, rotates and steams except partial solvent, adds appropriate distilled water, filters and obtains solid, and solid is used distilled water, methanol wash successively, after being dried, obtains described chlorine bridge dipolymer.
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 iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
Question response stops being chilled to after room temperature, and concentrated remove portion solvent, adds appropriate distilled water, has solid to separate out; Filter and collect crude product, crude product is used deionized water, methanol wash for several times successively, after the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol formation, 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 iridium metal complexes of blue light organic phosphorescent electroluminescent materials that adulterates in described luminescent layer, and general structure is as follows:
Wherein, R is hydrogen atom or C
1～C
20alkyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017088581A (en) * | 2015-11-17 | 2017-05-25 | 国立研究開発法人産業技術総合研究所 | Iridium complex and light emitting material and organic light emitting element prepared with the compound |
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| CN102807856A (en) * | 2011-06-01 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic electroluminescent material containing iridium and preparation method thereof, and organic electroluminescence device |
| CN102807854A (en) * | 2011-06-01 | 2012-12-05 | 海洋王照明科技股份有限公司 | Luminescent materials containing iridium and preparation method and application thereof |
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| CN102807856A (en) * | 2011-06-01 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic electroluminescent material containing iridium and preparation method thereof, and organic electroluminescence device |
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