CN104177421A - Blue light organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device - Google Patents
Blue light organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a blue light 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 description. In the structural general formula, R represents a hydrogen atom or alkyl of C1-C20. The blue light organic electrophosphorescent material iridium metal complex is synthesized by using 2-(2',6'-difluoropyridine-3'-yl)pyrimidine as cyclometalated ligands and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole as auxiliary ligands. Regulation of luminescent colors of the material is realized through chemical modification by introducing alkyl chains on pyrimidine rings of the cyclometalated ligands, and thus phosphorescence emission with wavelengths nearer to that of blue light can be obtained.
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, 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, 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 DEG C 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 1:1～1:1.5; 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 are dissolved in taking mol ratio as 2:1～4:1 in the mixed solvent of cellosolvo and water formation, heating mixed solvent is 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 contain sodium methylate or sodium ethylate taking mol ratio as 1:2～1:3 is dissolved in the second organic solvent in, obtain mixing solutions, heating mixing solutions to 40～84 DEG C, 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.
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 1:1～3:1.
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 0.02:1～0.05:1.
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 0.033～0.05mol/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 0.008～0.014mol/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, separates with the mixed solution that normal hexane forms taking ethyl acetate as elutriant carries out silica gel column chromatography, after being dried, obtains described cyclic metal complexes.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:5～1:10.
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'-difluoro pyridine-3'-yl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand.Be conducive to improve the lumo energy of material for electrical pyrimidine ring, the pyridine ring of short of electricity and encircle the HOMO energy level that two fluorine-based F of strong electron-withdrawing substituent are conducive to reduce material, makes the emission wavelength of material obtain effective blue shift; The difference of the electron-donating group alkoxyl group of the straight or branched formula of different lengths being introduced to pyrimidine ring replaces on position, except increasing the solubleness of material in organic solvent, and the space steric effect producing on pyrimidine ring can reduce outside the self-quenching phenomenon of triplet exciton in solid-state, the stronger emission wavelength of giving the further blue shift material of electronic effect energy, therefore can obtain higher luminous efficiency and blue light emitting wavelength; Simultaneously, on phenyl ring 4, two the strong fluorine-based F of electron substituent group and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1 of giving of 6-position, 2, the introducing of 4-triazole is blue shift emission wavelength effectively, different luminescent properties of joining type title complex can also, because intramolecular energy shifts be improved and improve, can reduce evaporation temperature, increases film-forming type and improves the stability of device.
A kind of 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.
Brief description of the drawings
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
Iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention, with 2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine 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 the chemically modified of introducing alkyl chain on the pyrimidine ring of cyclic metal complexes is realized to the adjusting to material glow color, thereby obtain the more blue phosphorescent emissions of emission wavelength.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:
or
; N=1～20.
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 DEG C 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 1:1～1:1.5; Wherein, 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 are dissolved in taking mol ratio as 2:1～4:1 in the mixed solvent of cellosolvo and water formation, heating mixed solvent is to reflux state stirring reaction 24h; 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; Reaction formula is:
Under S3, protection of inert gas, by described chlorine bridge dipolymer and structural formula be
compound C contain sodium methylate or sodium ethylate taking mol ratio as 1:2～1:3 is dissolved in the second organic solvent in, obtain mixing solutions, heating mixing solutions to 40～84 DEG C, 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; 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 1:1～3:1.
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 0.02:1～0.05:1.
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 0.033～0.05mol/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 0.008～0.014mol/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, separates as elutriant carries out silica gel column chromatography taking the mixed solution of ethyl acetate and normal hexane, after being dried, obtains described cyclic metal complexes.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:5～1:10.
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'-difluoro pyridine-3'-yl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand.Be conducive to improve the lumo energy of material for electrical pyrimidine ring, the pyridine ring of short of electricity and encircle the HOMO energy level that two fluorine-based F of strong electron-withdrawing substituent are conducive to reduce material, makes the emission wavelength of material obtain effective blue shift; The difference of the electron-donating group alkoxyl group of the straight or branched formula of different lengths being introduced to pyrimidine ring replaces on position, except increasing the solubleness of material in organic solvent, and the space steric effect producing on pyrimidine ring can reduce outside the self-quenching phenomenon of triplet exciton in solid-state, the stronger emission wavelength of giving the further blue shift material of electronic effect energy, therefore can obtain higher luminous efficiency and blue light emitting wavelength; Simultaneously, on phenyl ring 4, two the strong fluorine-based F of electron substituent group and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1 of giving of 6-position, 2, the introducing of 4-triazole is blue shift emission wavelength effectively, different luminescent properties of joining type title complex can also, because intramolecular energy shifts be improved and improve, can reduce evaporation temperature, 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.
A kind of 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'-difluoro 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'-difluoro pyridine-3'-yl) pyrimidine is synthetic
Under nitrogen protection; by 1.59g (10mmol) 2-bromo pyrimi piperidine (compd A 1), 1.91g (12mmol) 2; 6-difluoro pyridine-3-boric acid (compd B) and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, obtain reaction solution subsequently toward dripping 20mL in reaction system containing the aqueous solution of 2.76g (20mmol) salt of wormwood.Reacting by heating liquid, stirring reaction 8h under 100 DEG C 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.Ethyl acetate taking volume ratio as 1:5 separates as elutriant carries out silica gel column chromatography with the mixed solution of normal hexane, after being dried, obtains solid 1.16g, and yield is 60.0%.
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, 55.92; H, 2.67; F, 19.63; N, 21.78.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine
Under nitrogen protection, by 0.36g (1mmol) three hydration iridous chloride (IrCl
33H
2o) and 0.48g (2.5mmol) 2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine be dissolved in the mixed solvent that cellosolvo that 20mL volume ratio is 3:1 and water forms, 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 0.36g, and yield is 58.8%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-difluoro 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; be 2-(2' by 0.61g (0.5mmol) part; 6'-difluoro pyridine-3'-yl) pyrimidine containing iridium dichloro dimer and 0.27g (1.2mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1; 2; 4-triazole (Compound C) is dissolved in 20mL trichloromethane; drip subsequently the chloroform soln of 15mL containing 0.27g (5mmol) sodium methylate, stirring heating mixing solutions, is warming up to 62 DEG C of reflux state 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, obtains 0.44g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and yield is 55.7%.
Structural Identification:
Mass spectrum (MS m/z): 790.1 (M
+)
Ultimate analysis: C
26h
12f
7irN
10
Theoretical value: C, 39.55; H, 1.53; F, 16.84; Ir, 24.34; N, 17.74;
Measured value: C, 39.58; H, 1.48; F, 16.87; Ir, 24.31; N, 17.76.
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), two (2-(2', 6'-difluoro pyridine-3'-yl) 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 440nm place, has an acromion at 469nm place simultaneously, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, concentration is 10
-6two (2-(2', 6'-difluoro 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 is at 298K temperature, taking 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=0.32, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2: title complex two (2-(2', 6'-difluoro 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'-difluoro pyridine-3'-yl)-5-methylpyrimidine is synthetic
Under nitrogen protection; two to 1.73g (10mmol) the bromo-5-methylpyrimidine of 2-(A2), 1.59g (10mmol) compd B and 0.28g (0.4mmol) dichloro (triphenyl phosphorus) closed to palladium and be dissolved in 50mL DMF, obtain reaction solution toward dripping the aqueous solution that 25mL contains 3.18g (30mmol) sodium carbonate in reaction system subsequently.Stirring reaction 10h under reacting by heating liquid to 90 DEG C 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.Ethyl acetate taking volume ratio as 1:8 separates as elutriant carries out silica gel column chromatography with the mixed solution of normal hexane, after being dried, obtains solid 1.06g, and yield is 51.2%.
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, 57.91; H, 3.49; F, 18.28; N, 20.32.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-difluoro pyridine-3'-yl)-5-methylpyrimidine
Under nitrogen protection; by 0.36g (1mmol) three hydration iridous chlorides and 0.62g (2mmol) 2-(2'; 6'-difluoro pyridine-3'-yl) to be dissolved in 25mL volume ratio be in the cellosolvo of 3:1 and the mixed solvent of water to-5-methylpyrimidine, heating mixed solvent is to stirring 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 0.32g, and yield is 50.0%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-difluoro 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; be 2-(2' by 0.64g (0.5mmol) part; 4'-difluorophenyl) being dissolved in 30mL methylene dichloride containing iridium dichloro dimer and 0.21g (1mmol) Compound C of-5-methylpyrimidine; drip subsequently 15mL and obtain mixing solutions containing the dichloromethane solution of 0.27g (4mmol) sodium ethylate, stirring heating mixing solutions is warming up to 40 DEG C of reflux state 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, obtains 0.41g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and yield is 50.1%.
Structural Identification:
Mass spectrum (MS m/z): 818.1 (M
+)
Ultimate analysis: C
28h
16f
7irN
10
Theoretical value: C, 41.13; H, 1.97; F, 16.26; Ir, 23.51; N, 17.13;
Measured value: C, 41.17; H, 1.92; F, 16.28; Ir, 23.47; N, 17.16.
Two (2-(2', 6'-difluoro 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 445nm place, has an acromion at 475nm 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=0.19, visible the present embodiment there is higher luminous quantum efficiency containing iridium electroluminescent organic material, can be used as blue light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
Embodiment 3: title complex two (2-(2', 6'-difluoro 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'-difluoro pyridine-3'-yl)-5-tertiary butyl pyrimidine is synthetic
Under nitrogen protection; two to 2.15g (10mmol) 2-bromo-5-tertiary butyl pyrimidine (A3), 2.22g (14mmol) compd B and 0.21g (0.3mmol) dichloro (triphenyl phosphorus) closed to palladium and be dissolved in 35mL DMF, obtain reaction solution toward dripping the aqueous solution that 15mL contains 1.06g (10mmol) sodium carbonate in reaction system subsequently.Stirring reaction 12h under reacting by heating liquid to 85 DEG C 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.Ethyl acetate taking volume ratio as 1:8 separates as elutriant carries out silica gel column chromatography with the mixed solution of normal hexane, after being dried, obtains solid 0.80g, and yield is 32.1%.
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, 62.69; H, 5.20; F, 15.28; N, 16.83.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-difluoro pyridine-3'-yl)-5-tertiary butyl pyrimidine
Under nitrogen protection; by 0.36g (1mmol) three hydration iridous chlorides and 0.75g (3mmol) 2-(2'; 6'-difluoro pyridine-3'-yl) to be dissolved in 30mL volume ratio be in the cellosolvo of 3:1 and the mixed solvent of water to-5-tertiary butyl pyrimidine, 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 0.17g, and yield is 23.5%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-difluoro 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; be 2-(2' by 0.58g (0.4mmol) part; 6'-difluoro pyridine-3'-yl) being dissolved in 30mL trichloromethane containing iridium dichloro dimer and 0.21g (1mmol) Compound C of-5-tertiary butyl pyrimidine; drip subsequently 20mL and obtain mixing solutions containing the chloroform soln of 0.33g (4.8mmol) sodium ethylate, stirring heating mixing solutions is warming up to 62 DEG C of reflux state 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, obtains 0.30g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and yield is 41.6%.
Structural Identification:
Mass spectrum (MS m/z): 902.2 (M
+)
Ultimate analysis: C
34h
28f
7irN
10
Theoretical value: C, 45.28; H, 3.13; F, 14.75; Ir, 21.31; N, 15.53;
Measured value: C, 45.23; H, 3.19; F, 14.72; Ir, 21.35; N, 15.51.
Two (2-(2', 6'-difluoro 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 461nm place, has an acromion at 492nm 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=0.21.
Embodiment 4: title complex two (2-(2', 6'-difluoro 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'-difluoro pyridine-3'-yl)-4-eicosyl pyrimidine is synthetic
Under nitrogen protection; the bromo-4-eicosyl of 2.20g (5mmol) 2-pyrimidine (compd A 4), 1.19g (7.5mmol) compd B and 0.12g (0.1mmol) four (triphenyl phosphorus) are closed to palladium and be dissolved in 35mL toluene, obtain reaction solution toward dripping 15mL in reaction system containing the aqueous solution of 1.73g (12.5mmol) salt of wormwood subsequently.Stirring reaction 15h under reacting by heating liquid to 85 DEG C 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.Ethyl acetate taking volume ratio as 1:10 separates as elutriant carries out silica gel column chromatography with the mixed solution of normal hexane, after being dried, obtains solid 0.43g, and yield is 18.2%.
Structural Identification:
Mass spectrum (MS m/z): 473.4 (M
+)
Ultimate analysis: C
29h
45f
2n
3
Theoretical value: C, 73.53; H, 9.58; F, 8.02; N, 8.87;
Measured value: C, 73.56; H, 9.52; F, 8.10; N, 8.82.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(2', 6'-difluoro pyridine-3'-yl)-4-eicosyl pyrimidine
Under nitrogen protection; by 0.18g (0.5mmol) three hydration iridous chlorides and 0.88g (2mmol) 2-(2'; 6'-difluoro pyridine-3'-yl) to be dissolved in 10mL volume ratio be in the cellosolvo of 3:1 and the mixed solvent of water to-4-eicosyl pyrimidine, 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 0.07g, and yield is 14.8%.Dipolymer, without further purification, can directly drop in next step reaction.
(3) two (2-(2', 6'-difluoro 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; be 2-(2' by 0.57g (0.3mmol) part; 6'-difluoro pyridine-3'-yl)-4-eicosyl pyrimidine be 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 obtains mixing solutions, and stirring heating mixing solutions is warming up to 84 DEG C 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, obtains 0.10g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and yield is 12.3%.
Structural Identification:
Mass spectrum (MS m/z): 1350.1 (M
+)
Ultimate analysis: C
66h
92f
7irN
10
Theoretical value: C, 58.69; H, 6.87; F, 9.85; Ir, 14.23; N, 10.37;
Measured value: C, 58.65; H, 6.92; F, 9.80; Ir, 14.28; N, 10.35.
Two (2-(2', 6'-difluoro pyridine-3'-yl)-6-eicosyl 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 471nm place, has an acromion at 501nm 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.
Application Example
The present embodiment is organic electroluminescence device, its title complex making with embodiment 1 two (2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine-N, C
4') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close iridium (representing using M1) as luminescent layer doping guest materials; Structural formula is:
As shown in Figure 3, the structure of organic electroluminescence device 300 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 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 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.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), 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 445nm, has an acromion at 475nm place, and maximum current efficiency is 9.0cd/A, and maximum external quantum efficiency is 6.8%.
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 DEG C 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 1:1～1:1.5; 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 are dissolved in taking mol ratio as 2:1～4:1 in the mixed solvent of cellosolvo and water formation, heating mixed solvent is 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 contain sodium methylate or sodium ethylate taking mol ratio as 1:2～1:3 is dissolved in the second organic solvent in, obtain mixing solutions, heating mixing solutions to 40～84 DEG C, 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 1:1～3:1.
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 0.02:1～0.05:1.
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 0.008～0.014mol/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, separates with the mixed solution that normal hexane forms taking ethyl acetate as elutriant carries out silica gel column chromatography, after being dried, obtains described cyclic metal complexes.
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, 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.
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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| CN1664054A (en) * | 2004-02-02 | 2005-09-07 | 三星Sdi株式会社 | IR compound and organic electroluminescent device using the same |
| CN102307886A (en) * | 2009-02-06 | 2012-01-04 | 索尔维公司 | Phosphorescent light-emitting iridium complex containing pyridyltriazole ligand |
| 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 |
-
2013
- 2013-05-22 CN CN201310193005.6A patent/CN104177421A/en active Pending
Patent Citations (4)
| 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 |
| CN102307886A (en) * | 2009-02-06 | 2012-01-04 | 索尔维公司 | Phosphorescent light-emitting iridium complex containing pyridyltriazole ligand |
| 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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