CN104342117A - Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device - Google Patents
Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device Download PDFInfo
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- CN104342117A CN104342117A CN201310329661.4A CN201310329661A CN104342117A CN 104342117 A CN104342117 A CN 104342117A CN 201310329661 A CN201310329661 A CN 201310329661A CN 104342117 A CN104342117 A CN 104342117A
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Abstract
The invention relates to an organic electro-phosphorescent material and a preparation method thereof, and an organic electroluminescent device. The organic electro-phosphorescent material (P) has a following structure, wherein R is phenyl group, fluorenyl group or carbazolyl group. According to the organic electro-phosphorescent material, a blue-light organic electro-phosphorescent material iridium metal complex is synthesized with 2-(2',3',4'-trifluorophenyl)pyrimidine as a cyclo-metal ligand and with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole as a subsidiary ligand. The adjustment upon material luminescent colors is realized through introducing phenyl group, fluorenyl group or carbazolyl group chemical modification to the pyrimidine ring of the cyclo-metal ligand, such that high-luminous-efficiency blue phosphorescent emission is obtained.
Description
Technical field
The present invention relates to field of light emitting materials, particularly relate to a kind of organic electromechanical phosphorescent material.The invention still further relates to the preparation method of this organic electromechanical phosphorescent material and its application in 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.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq3) for luminescent material, the high-quality thin film of even compact is made with aromatic diamine, obtain low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, 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 hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, 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 the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.And in order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Compare with green light material with ruddiness, the development of blue light material is more delayed comparatively speaking, the breakthrough point that the efficiency improving blue light material has just become people to study with purity of color.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of organic electromechanical phosphorescent material and preparation method thereof and organic electroluminescence device are provided, this organic electromechanical phosphorescent material is with 2-(2', 3', 4'-trifluorophenyl) pyrimidine is cyclic metal complexes, with 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole is assistant ligand, synthesize a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and by introducing phenyl on the pyrimidine ring of cyclic metal complexes, the chemically modified of fluorenyl or carbazyl realizes the adjustment to material emission color, thus obtain the blue phosphorescent emission of high-luminous-efficiency.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is: one has the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R is phenyl, fluorenyl or carbazyl.
The invention still further relates to a kind of preparation method of organic electromechanical phosphorescent material, the method comprises the following steps:
A) following compd A and B is provided;
Compd A is
compd B is
B) under atmosphere of inert gases, described compd A and described compd B are added in organic solvent according to the mol ratio of 1:2 ~ 3, drip the identical organic solvent containing alkoxide subsequently again, ligand exchange reaction is carried out 8 ~ 20 hours at being heated to 40 ~ 83 DEG C, naturally after being chilled to room temperature, separating-purifying, obtains the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R is phenyl, fluorenyl or carbazyl.
In step (b), described compd A and described alkoxide mol ratio be 1:8 ~ 12; Described organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane; Described alkoxide is sodium methylate or sodium ethylate; The concentration range of described compd A in described organic solvent is 0.01 ~ 0.02mol/L.
Further, described compd A adopts following steps to obtain:
C) following Compound C and D is provided:
Compound C is
compound D is three hydrated iridium trichloride,
Wherein, R is phenyl, fluorenyl or carbazyl;
D) under atmosphere of inert gases, described Compound C and described Compound D are added in the aqueous solution of cellosolvo according to the mol ratio of 2 ~ 3:1, the concentration range of wherein said Compound C in described cellosolvo is 0.02 ~ 0.033mol/L, be heated to stirring reaction 24h under reflux state, after being chilled to room temperature, rotation is steamed except partial solvent, after adding distilled water filtration, then obtains described compd A with after distilled water, methanol wash drying successively.
Described Compound C adopts following steps to obtain:
G) following compd E and F is provided:
Compd E is
compound F 17-hydroxy-corticosterone is 2,3,4-trifluoro-benzene boric acid,
Wherein, R is phenyl, fluorenyl or carbazyl;
H) under atmosphere of inert gases, described compd E and described compound F 17-hydroxy-corticosterone are added toluene containing palladium catalyst or N according to the mol ratio of 1:1 ~ 1.5, in the solution of dinethylformamide, then drip alkaline catalysts to reheat, Suzuki linked reaction 10 ~ 15h at 85 ~ 100 DEG C of temperature, after being chilled to room temperature, separating-purifying, obtains described Compound C.
At described step f) in, described separating-purifying step is as follows: the reaction solution that described Suzuki linked reaction obtains is poured in methylene dichloride carry out extracting, separatory, and be washed to neutrality, filter with after anhydrous magnesium sulfate drying again, filtrate decompression steams solvent and obtains crude product, be separated for elutriant carries out silica gel column chromatography with normal hexane with ethyl acetate again, after drying, obtain described Compound C.
At described step f) in, described palladium catalyst is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium; Described alkaline catalysts is salt of wormwood or sodium carbonate.
The mol ratio of described palladium catalyst and described compd E is 0.04 ~ 0.06:1; The mol ratio of described alkaline catalysts and described compd E is 1.5 ~ 2.5:1; In the solution of described toluene or DMF, the volume ratio of solute and water is 2:1; The concentration of described compd E in described organic solvent is 0.11 ~ 0.14mol/L.
The invention still further relates to a kind of organic electroluminescence device, it comprises anode, functional layer, luminescent layer and negative electrode, and the material of described luminescent layer is above-mentioned organic electromechanical phosphorescent material.
Compared with prior art, there is following advantage in organic electromechanical phosphorescent material of the present invention and preparation method thereof and organic electroluminescence device:
Organic electromechanical phosphorescent material of the present invention is assistant ligand with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles for assistant ligand.On the pyrimidine ring of the planar rigidity on main part and phenyl ring, the C-F key of low vibrational frequency is conducive to reducing nonradiative transition probability, improves the luminous efficiency of material; After pyrimidine ring being introduced the aromatic groups such as phenyl, fluorenyl, carbazyl, the electro mass-energy of giving of the aromatic groups such as one side phenyl, fluorenyl, carbazyl regulates blue light emitting wavelength, the aromatic group such as phenyl, fluorenyl, carbazyl of large volume can produce larger space steric effect on the one hand in addition, the direct effect between atoms metal can be reduced, reduce the self-quenching phenomenon of triplet exciton, thus the luminous efficiency of material is improved; Fluorine-based and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1,2, the 4-triazole of strong electron-withdrawing group group on phenyl ring is introduced and can be improved luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
Accompanying drawing explanation
Fig. 1 is the utilizing emitted light spectrogram of the Phosphorescent luminescent material of preparation in the embodiment of the present invention 1.
Fig. 2 is the structural representation of the organic electroluminescence device of preparation in the embodiment of the present invention 4.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Organic electromechanical phosphorescent material of the present invention has following general formula (P):
Wherein, R is phenyl, fluorenyl or carbazyl, and the position of substitution can in 4-or the 5-position of pyrimidine.
The invention still further relates to a kind of preparation method of above-mentioned organic electromechanical phosphorescent material, the method comprises the following steps successively:
1, make compd E and compound F 17-hydroxy-corticosterone by Suzuki linked reaction synthetic compound C; Wherein, compound F 17-hydroxy-corticosterone is 2,3,4-trifluoro-benzene boric acid, and the structural formula of compd E and Compound C is as follows:
Compd E is
compound C is
2, Compound C step 1 obtained and Compound D are reacted and are generated chlorine bridge dipolymer, i.e. compd A.Wherein, Compound D is three hydrated iridium trichloride IrCl
33H
2o.The structural formula of compd A is as follows:
3, compd A obtained for step 2 is used as cyclic metal complexes agent structure, by 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole (compd B) is as assistant ligand source, compd A and compd B is made to react to obtain iridium metal complex, i.e. organic electromechanical phosphorescent material (P):
Above in each step, described R is phenyl, fluorenyl or carbazyl; Rare gas element is one or more in nitrogen, helium or neon.
Synthetic route is:
Namely 2-, 3-, 4-position respectively with the fluorine-based phenyl ring of electrophilic and pyrimidine or its derivative replaced with alkyl by Suzuki linked reaction synthesizing ring metal part, then with IrCl
33H
2o reaction generates chlorine bridge dipolymer, and last and assistant ligand source 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles react obtained target iridium metal complex.
Be specifically described with embodiment below:
Embodiment 1
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two (2-(4', 5', 6'-trifluoromethyl phenyl)-5-phenyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium, its structural formula is as follows:
It obtains as follows:
(1) synthesis of 2-(2', 3', 4'-trifluorophenyl)-5-phenyl pyrimidine
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, by bromo-for 2.35g (10mmol) 2-5-phenyl pyrimidine, 2.11g (12mmol) 2, 3, 4-trifluoro-benzene boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 50ml toluene, the aqueous solution of 25ml containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system, be heated to stirring reaction 10h under 100 DEG C of state of temperatures, after question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying, after filtration, filtrate decompression steams solvent and obtains crude product, with volume ratio be 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, solid 2-(2' is obtained after drying, 3', 4'-trifluorophenyl)-5-phenyl pyrimidine 1.17g, yield is 40.9%.
Structural Identification is carried out to described solid: mass spectrum (MS m/z): 286.1 (M
+); Ultimate analysis is carried out to described solid: molecular formula is C
16h
9f
3n
2, wherein, theoretical value is: C, 67.13; H, 3.17; F, 19.91; N, 9.79, measured value is: C, 67.08; H, 3.22; F, 19.88; N, 9.82.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 3', 4'-trifluorophenyl)-5-phenyl pyrimidine.
(2) part be 2-(2', 3', 4'-trifluorophenyl)-5-phenyl pyrimidine containing the dimeric synthesis of iridium dichloro
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride, 0.72g (2.5mmol) 2-(2', 3', 4'-trifluorophenyl) to be dissolved in 30ml volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-phenyl pyrimidine, is heated to stirring reaction 24h under reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.28g after drying, yield is 35.1%, part is 2-(2', 3', 4'-trifluorophenyl)-5-phenyl pyrimidine containing iridium dichloro dimer without the need to further purification, can directly drop into next step reaction in.
(3) title complex two (2-(4', 5', 6'-trifluoromethyl phenyl)-5-phenyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, be 2-(2' by 0.80g (0.5mmol) part, 3', 4'-trifluorophenyl)-5-phenyl pyrimidine containing iridium dichloro dimer and 0.27g (1.25mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole is dissolved in 15ml1, in 2-ethylene dichloride, drip 10ml subsequently containing 1 of 0.27g (5mmol) sodium methylate, 2-dichloroethane solution, stirring heating is warming up to 84 DEG C of reflux state reaction 8h, naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, then filter, collect crude product, solid uses deionized water successively, methanol wash for several times, 0.29g pure products is obtained through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 29.7%.
Structural Identification: mass spectrum (MS m/z): 976.1 (M
+).Ultimate analysis is carried out to described solid: C
40h
20f
9irN
8, theoretical value: C, 49.23; H, 2.07; F, 17.52; Ir, 19.70; N, 11.48; Measured value: C, 49.27; H, 2.02; F, 17.55; Ir, 19.66; N, 11.50.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4', 5', 6'-trifluorophenyl))-5-phenyl pyrimidine-N, the C of title complex
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium.
As shown in Figure 2, transverse axis is wavelength (Wavelength, unit nm), 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 470nm place, has an acromion at 495nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-6the CH of M end product
2cl
2solution at 298K temperature, with concentration for ~ 10
-6the CH of the FIrpic of M
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.14, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two (2-(4', 5', 6'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine-N, C
2') (2-pyridinecarboxylic) close iridium, its structural formula is as follows:
It obtains as follows:
(1) title complex two (2-(4', 5', 6'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine-N, C
2') (2-pyridinecarboxylic) close the synthesis of iridium
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, by the bromo-4-of 3.23g (10mmol) 2-(fluorenes-9 '-Ji) pyrimidine, 1.76g (10mmol) 2,3,4-trifluoro-benzene boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) close the N that palladium is dissolved in 60ml, in dinethylformamide (DMF), the aqueous solution of 30ml containing 1.59g (15mmol) sodium carbonate is dripped subsequently in reaction system, be heated to stirring reaction 12h under 90 DEG C of states, after question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 3:1 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, two (2-(the 4' of solid is obtained after drying, 5', 6'-trifluorophenyl) and-4-(fluorenes-9 '-Ji) pyrimidine-N, C2') (2-pyridinecarboxylic) closes iridium 1.31g, and yield is 35.0%.
Structural Identification is carried out to described solid: mass spectrum (MS m/z): 374.1 (M
+).Ultimate analysis is carried out to described solid: molecular formula is C
23h
13f
3n
2, theoretical value: C, 73.79; H, 3.50; F, 15.22; N, 7.48; Measured value: C, 73.74; H, 3.59; F, 15.13; N, 7.54.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 3', 4'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine.
(2) part be 2-(2', 3', 4'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine containing the dimeric synthesis of iridium dichloro
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, by 0.35g (1mmol) three hydrated iridium trichloride and 1.12g (3mmol) 2-(2', 3', 4'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine is dissolved in 40ml2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux, after being chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter, solid uses distilled water successively, methanol wash, solids 0.29g is obtained after drying, yield is 29.8%, product 2-(2', 3', 4'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine containing iridium dichloro dimer without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(4', 5', 6'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, be 2-(2' by 0.78g (0.4mmol) part, 3', 4'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine containing iridium dichloro dimer and 0.17g (0.8mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole is dissolved in 15ml methylene dichloride, drip the dichloromethane solution of 10ml containing 0.22g (3.2mmol) sodium ethylate subsequently, stirring heating is warming up to 40 DEG C of reflux state reaction 20h, naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, crude product is collected after filtration, solid uses deionized water successively, methanol wash for several times, 0.17g pure products is obtained through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 18.4%.
Structural Identification is carried out to described solid: mass spectrum (MS m/z): 1152.2 (M
+), ultimate analysis is carried out to described solid: C
54h
28f
9irN
8, theoretical value: C, 56.30; H, 2.45; F, 14.84; Ir, 16.68; N, 9.73; Measured value: C, 56.35; H, 2.41; F, 14.79; Ir, 16.70; N, 9.75.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4', 5', 6'-trifluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 480nm place, has an acromion at 505nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.12.
Embodiment 3
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two (2-(4', 5', 6'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium, its structural formula is as follows:
It obtains as follows:
(1) synthesis of 2-(2', 3', 4'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, by the bromo-5-of 1.62g (5mmol) 2-(carbazole-N-base) pyrimidine, 1.32g (7.5mmol) 2,3,4-trifluoro-benzene boric acid and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 24ml toluene, drip the aqueous solution of 12ml containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 15h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying, after filtration, filtrate decompression steams solvent and obtains crude product, be that the ethyl acetate of 5:1 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 2-(2', 3', 4'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine 0.56g, yield is 29.8%.
Structural Identification is carried out to described solid: mass spectrum (MS m/z): 375.1 (M
+).Ultimate analysis is carried out to described solid: C
22h
12f
3n
3, theoretical value: C, 70.40; H, 3.22; F, 15.18; N, 11.20; Measured value: C, 70.44; H, 3.17; F, 15.25; N, 11.14.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 3', 4'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine.
(2) part be 2-(2', 3', 4'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine containing the dimeric synthesis of iridium dichloro
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, 0.18g (0.5mmol) three hydrated iridium trichloride, 0.75g (2mmol) 2-(2', 3', 4'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine is dissolved in 50ml2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.26g after drying, yield is 26.6%, and dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(4', 5', 6'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine-N, C2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) closes the synthesis of iridium
The reaction formula of synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, be 2-(4' by 0.58g (0.3mmol) part, 5', 6'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine containing iridium dichloro dimer and 0.19g (0.9mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole is dissolved in 20ml trichloromethane, drip the chloroform soln of 10ml containing 0.19g (3.6mmol) sodium ethylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 15h, naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, solid is had to separate out, then collecting by filtration crude product, solid uses deionized water successively, methanol wash for several times, 0.12g pure products is obtained through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 17.3%.
Structural Identification: mass spectrum (MS m/z): 1154.2 (M
+).Ultimate analysis is carried out to described solid: C
52h
26f
9irN
10, theoretical value: C, 54.12; H, 2.27; F, 14.82; Ir, 16.66; N, 12.14; Measured value: C, 54.07; H, 2.33; F, 14.78; Ir, 16.69; N, 12.13.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4', 5', 6'-trifluorophenyl)-5-(carbazole-N-base) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 475nm place, has an acromion at 500nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.10.
Embodiment 4
With the title complex that embodiment 1 is obtained two (2-(4', 5', 6'-trifluorophenyl)-5-phenyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium as luminescent layer doping object organic electroluminescence device, its structure as shown in Figure 2:
This organic electroluminescence device comprise stack gradually substrate, anode layer, hole injection layer 302, hole transmission layer 303, electronic barrier layer 304, luminescent layer 305, hole blocking layer 306, electron transfer layer 307, buffer layer 308 and cathode layer 309.Wherein:
Substrate adopts glass (Glass), and the material of anode layer is that ITO, ITO are prepared in glass surface, is called for short ito glass together with glass.Certainly, the material of anode layer also can be FTO, AZO, IZO.Be preferably the ITO(tin indium oxide that square resistance is 10-20 Ω), thickness is 200nm;
The material of hole injection layer 302 is m-MTDATA(4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine), thickness 40nm;
The material of hole transmission layer 303 is two (1-naphthyl)-N, the N'-diphenylbenzidine of NPB(N, N'-), thickness 20nm;
The material of electronic barrier layer 304 is two (9-carbazyl) benzene of mCP(1,3-), thickness 10nm;
The material of luminescent layer 305 is two (2-(4', 5', 6'-trifluorophenyl)-5-phenyl pyrimidine-N, the C that prepare doped with 7wt% embodiment 1
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the mCP of iridium, thickness 30nm;
The material of hole blocking layer 306 is BCP(2,9-dimethyl-4,7-phenylbenzene-phenanthrolene), thickness 10nm;
The material of electron transfer layer 307 is Alq
3(three (oxine) aluminium), thickness is 35nm;
The material of buffer layer 308 is LiF, thickness 1nm;
The material of cathode layer 309 is Al layer, thickness 120nm.
The structure of this organic electroluminescence device is: ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%Ir title complex (30nm)/BCP (10nm)/Alq3 (35nm)/LiF (1nm)/Al (120nm); Wherein, brace "/" represents laminate structure, and the colon ": " in P1:FIrpic represents doping.
The preparation technology of this organic electroluminescence device is as follows:
Glass-based plate deposits a layer thickness is 200nm, square resistance is 10 ~ 20 Ω tin indium oxide (ITO) as transparent anode 301;
On anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, two (1-the naphthyl)-N of N'-, N'-diphenylbenzidine) hole mobile material is as hole transmission layer 303, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is as electronic barrier layer 304, with the two (2-(4' prepared doped with 7wt% embodiment 1 that a layer thickness is 30nm, 5', 6'-trifluorophenyl)-5-phenyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the mCP of iridium as luminescent layer 305,
On this luminescent layer 305, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) material be the Alq3 (three (oxine) aluminium) of 35nm as hole blocking layer 306, thickness is that the LiF of 1nm is as electron injection buffer layer 308 as electron transfer layer 307, thickness, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metal A l of 120nm, as the negative electrode 309 of device.
After tested, the maximum external quantum efficiency of this organic electroluminescence device is 5.6%, and maximum current efficiency is 7.1cd/A, and the more existing organic electroluminescence device of this organic electroluminescence device has higher luminous efficiency.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (10)
1. the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R is phenyl, fluorenyl or carbazyl.
2. a preparation method for organic electromechanical phosphorescent material, the method comprises the following steps:
A) following compd A and B is provided;
Compd A is
compd B is
B) under atmosphere of inert gases, described compd A and described compd B are added in organic solvent according to the mol ratio of 1:2 ~ 3, drip the identical organic solvent containing alkoxide subsequently again, ligand exchange reaction is carried out 8 ~ 20 hours at being heated to 40 ~ 83 DEG C, naturally after being chilled to room temperature, separating-purifying, obtains the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R is phenyl, fluorenyl or carbazyl.
3. preparation method according to claim 3, is characterized in that, in step (b), described compd A and described alkoxide mol ratio be 1:8 ~ 12; Described organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane; Described alkoxide is sodium methylate or sodium ethylate; The concentration range of described compd A in described organic solvent is 0.01 ~ 0.02mol/L.
4. preparation method according to claim 2, it is characterized in that, in step (b), described separating-purifying step is as follows: after the reaction solution that described ligand exchange reaction obtains is chilled to room temperature naturally, and concentrated remove portion solvent, adds distilled water, filter after separating out solid, collect crude product, described solid uses deionized water, methanol wash for several times successively, then through methylene dichloride and dehydrated alcohol mixed solvent recrystallization.
5. preparation method according to claim 4, is characterized in that, described compd A adopts following steps to obtain:
C) following Compound C and D is provided:
Compound C is
compound D is three hydrated iridium trichloride,
Wherein, R is phenyl, fluorenyl or carbazyl;
D) under atmosphere of inert gases, described Compound C and described Compound D are added in the aqueous solution of cellosolvo according to the mol ratio of 2 ~ 3:1, the concentration range of wherein said Compound C in described cellosolvo is 0.02 ~ 0.033mol/L, be heated to stirring reaction 24h under reflux state, after being chilled to room temperature, rotation is steamed except partial solvent, after adding distilled water filtration, then obtains described compd A with after distilled water, methanol wash drying successively.
6. preparation method according to claim 5, is characterized in that, described Compound C adopts following steps to obtain:
E) following compd E and F is provided:
Compd E is
compound F 17-hydroxy-corticosterone is 2,3,4-trifluoro-benzene boric acid,
Wherein, R is phenyl, fluorenyl or carbazyl;
F) under atmosphere of inert gases, described compd E and described compound F 17-hydroxy-corticosterone are added toluene containing palladium catalyst or N according to the mol ratio of 1:1 ~ 1.5, in the solution of dinethylformamide, then drip alkaline catalysts to reheat, Suzuki linked reaction 10 ~ 15h at 85 ~ 100 DEG C of temperature, after being chilled to room temperature, separating-purifying, obtains described Compound C.
7. preparation method according to claim 6, it is characterized in that, at described step f) in, described separating-purifying step is as follows: the reaction solution that described Suzuki linked reaction obtains is poured in methylene dichloride carry out extracting, separatory, and be washed to neutrality, then filter with after anhydrous magnesium sulfate drying, filtrate decompression steams solvent and obtains crude product, be separated for elutriant carries out silica gel column chromatography with normal hexane with ethyl acetate again, after drying, obtain described Compound C.
8. preparation method according to claim 6, is characterized in that, at described step f) in, described palladium catalyst is that four (triphenyl phosphorus) close palladium or two chlorine two (triphenyl phosphorus) closes palladium; Described alkaline catalysts is salt of wormwood or sodium carbonate.
9. preparation method according to claim 6, is characterized in that, the mol ratio of described palladium catalyst and described compd E is 0.04 ~ 0.06:1; The mol ratio of described alkaline catalysts and described compd E is 1.5 ~ 2.5:1; In the solution of described toluene or DMF, the volume ratio of solute and water is 2:1; The concentration of described compd E in described organic solvent is 0.11 ~ 0.14mol/L.
10. an organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that, the material of described luminescent layer is organic electromechanical phosphorescent material according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632488A (en) * | 2016-09-08 | 2017-05-10 | 安徽工业大学 | Sterically-hindered pyrimidine iridium complex phosphorescence material and preparation method thereof |
| JP2018118981A (en) * | 2011-10-06 | 2018-08-02 | 株式会社半導体エネルギー研究所 | Organic compound |
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2013
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018118981A (en) * | 2011-10-06 | 2018-08-02 | 株式会社半導体エネルギー研究所 | Organic compound |
| CN106632488A (en) * | 2016-09-08 | 2017-05-10 | 安徽工业大学 | Sterically-hindered pyrimidine iridium complex phosphorescence material and preparation method thereof |
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Application publication date: 20150211 |