CN104293342A - Blue-light organic electrophosphorescent material, preparation method and application thereof - Google Patents
Blue-light organic electrophosphorescent material, preparation method and application thereof Download PDFInfo
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- CN104293342A CN104293342A CN201310300743.6A CN201310300743A CN104293342A CN 104293342 A CN104293342 A CN 104293342A CN 201310300743 A CN201310300743 A CN 201310300743A CN 104293342 A CN104293342 A CN 104293342A
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- 0 *C1N=C(C(CC(F)=C2F)C=C2F)N=CC1 Chemical compound *C1N=C(C(CC(F)=C2F)C=C2F)N=CC1 0.000 description 3
- SILKXKOPYJDPCJ-UHFFFAOYSA-N Bc1ncc(C)cn1 Chemical compound Bc1ncc(C)cn1 SILKXKOPYJDPCJ-UHFFFAOYSA-N 0.000 description 1
- WRLBUOIBBUZJGP-UHFFFAOYSA-N CCCCCC(CC(F)=C1F)C=C1F Chemical compound CCCCCC(CC(F)=C1F)C=C1F WRLBUOIBBUZJGP-UHFFFAOYSA-N 0.000 description 1
- NNDOMNOJRTWEBU-UHFFFAOYSA-N Cc1cnc(-c(cc2F)cc(F)c2F)nc1 Chemical compound Cc1cnc(-c(cc2F)cc(F)c2F)nc1 NNDOMNOJRTWEBU-UHFFFAOYSA-N 0.000 description 1
- PITQKYAUZKIFFG-UHFFFAOYSA-N Fc(cc(CB1CC1)cc1F)c1F Chemical compound Fc(cc(CB1CC1)cc1F)c1F PITQKYAUZKIFFG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a blue-light organic electrophosphorescent material having a following structure formula, wherein -R is -H, an alkyl group with a general formula being -C<n>H<2n+1> or an alkoxy group with a general formula being -OC<n>H<2n+1>, wherein n is an integer being 1-20. In the blue-light organic electrophosphorescent material, 2-(3',4',5'-trifluorophenyl)pyrimidine is a cyclometal ligand major structure and tetra(1-pyrazol) boron as an auxiliary ligand. A flat rigid pyrimidine ring on the major ligand and a low-vibration-frequency C-F bond on a benzene ring are beneficial for reduction of non-radiative transition probability so that a luminous efficiency of the blue-light organic electrophosphorescent material is improved. The invention also provides a preparation method of the blue-light organic electrophosphorescent material.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly relate to a kind of blue light organic phosphorescent electroluminescent materials and preparation method thereof and application.
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 the U.S. understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained 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.
The people such as Holmes R J, Forrest S R, at App.Phys.Lett., disclose two [2-(4', 6'-difluorophenyl) pyridine-N, C in 2003,82 (15): 2422-2424 articles
2'] (2-pyridinecarboxylic) close iridium (FIrpic), be at present report at most, be also the best blue light organic phosphorescent electroluminescent materials of over-all properties, its structural formula is as follows:
Although people have carried out various optimization to FIrpic class OLED structure, device performance have also been obtained very large raising, but the maximum weakness of FIrpic is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED made is (0.13 ~ 0.17,0.29 ~ 0.39) change between, between this and standard blue light CIE (0.137,0.084), have very large gap.
The people such as Holmes R J, Forrest S R disclose and change with four (1-pyrazoles) blue phosphorescent iridium metal complex luminescent material two [2-(4', 6'-difluorophenyl) pyridine-N, the C that boron is assistant ligand
2'] (four (1-pyrazoles) change boron) close iridium (FIr6) (App.Phys.Lett., 2003,83:3818-3820.), the CIE being entrained in the OLED in the wide energy gap material of main part of high triplet UGH1 or UGH2 is (0.16,0.26), compare with (0.16,0.37) of the FIrpic device of identity unit structure, blue light color purity is improved.The introducing blue shift emission wavelength of material effectively that high field intensity assistant ligand four (1-pyrazoles) changes boron, blue light color purity is higher, becomes one of first-selected assistant ligand of different distribution type blue phosphorescent complex of iridium luminescent material.The structural formula of FIr6 is as follows:
2011, the Zhang Xiaohong seminar of physiochemical techniques institute of the Chinese Academy of Sciences report in a kind of cyclic metal complexes containing trifluorophenyl structure containing complex of iridium blue phosphor materials-bis-[2-(3', 4', 5'-trifluorophenyl) pyridine-N, C
2'] (2-pyridinecarboxylic) close iridium (F
3irpic) [Organic Electronics12 (2011) 2061-2064].Under same test condition, although F
3the maximum emission wavelength of Irpic is FIrpic red shift 8nm comparatively, but its phosphorescence quantum yield compared with FIrpic reference standard 0.50 brought up to 0.67.F
3the structural formula of Irpic is as follows:
Along with going deep into of the research to organic electromechanical phosphorescent material iridium metal complex, there is bottleneck problem in traditional blue emitting phosphor material in luminous efficiency etc.Therefore, the blue phosphorescent organic electroluminescent material developing high-luminous-efficiency is significant in expansion blue light material research field.
Summary of the invention
Based on this, be necessary to provide blue light organic phosphorescent electroluminescent materials that a kind of luminous efficiency is higher and preparation method thereof.
In addition, there is a need to the organic electroluminescence device that a kind of blue light organic phosphorescent electroluminescent materials adopting luminous efficiency higher is provided.
A kind of blue light organic phosphorescent electroluminescent materials, has following structural formula:
Wherein ,-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20.
In one embodiment, the structural formula of described blue light organic phosphorescent electroluminescent materials is:
A preparation method for blue light organic phosphorescent electroluminescent materials, comprises the steps:
The Compound D with following structural formula is provided,
wherein-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20;
Under shielding gas atmosphere, by described Compound D and IrCl
33H
2o is dissolved in the first solvent, and stirring reaction 22h ~ 25h, obtains compd E after separation and purification at reflux, and the structural formula of described compd E is as follows,
wherein, described Compound D and IrCl
33H
2the mol ratio of O is 2 ~ 4:1;
Under described shielding gas atmosphere, described compd E is dissolved in the second solvent, at room temperature drips the organic solution of Ag organic salt, filter after reacting completely, remove the solvent in described filtrate after retaining filtrate, obtain solid residues;
Under described shielding gas atmosphere; described solid residues and compound G are dissolved in the 3rd solvent, back flow reaction 22h ~ 25h, obtains blue light organic phosphorescent electroluminescent materials after separation and purification; the structural formula of described compound G and described blue light organic phosphorescent electroluminescent materials is as follows
blue light organic phosphorescent electroluminescent materials:
wherein, the mol ratio of described compd E and described compound G is 1:2 ~ 3.
In one embodiment, described Compound D prepares as follows,
The compounds X and compound Y with following structural formula are provided,
In described shielding gas atmosphere; under catalyzer, alkali lye and organic solvent existent condition; by described compounds X and described compound Y, return stirring 6h ~ 12h at 85 DEG C ~ 100 DEG C carries out Suzuki coupling reaction; described Compound D is obtained after separation and purification; wherein, the mol ratio of described compounds X and described compound Y is 1:1 ~ 1.5.
In one embodiment,
Described catalyzer is Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, the mol ratio of described catalyzer and described compounds X is 2:5 ~ 100;
Described alkali lye is Na
2cO
3or K
2cO
3the aqueous solution, in described alkali lye, the mole number of solute and the mol ratio of described compounds X are 1:3 ~ 1;
Described organic solvent is toluene, tetrahydrofuran (THF) or DMF;
Described compounds X concentration is in organic solvent 0.1mol/L ~ 0.2mol/L.
In one embodiment, the structural formula of described Compound D is:
In one embodiment, described shielding gas atmosphere is nitrogen atmosphere or atmosphere of inert gases;
Described first solvent is volume ratio is the cellosolvo of 3:1 and the mixed solution of water;
The concentration of described Compound D in described first solvent is 0.1mol/L ~ 0.2mol/L;
Described second solvent is methylene dichloride or trichloromethane;
In the organic solution of described Ag organic salt, Ag organic salt is trifluoroacetic acid silver, and solvent is methyl alcohol, and the mol ratio of described Ag organic salt and described compd E is 2 ~ 3:1;
Described 3rd solvent is acetonitrile;
The concentration of described compd E in described 3rd solvent is 0.01mol/L ~ 0.025mol/L.
In one embodiment, after described separation and purification, obtain being operating as of compd E: after mixed system remove portion solvent, add distilled water precipitating, after filtration, retain filter residue, and use distilled water and methanol wash successively, after drying, obtain described compd E.
In one embodiment, being operating as of blue light organic phosphorescent electroluminescent materials is obtained: mixed system filters after being cooled to room temperature after described separation and purification, retain filtrate and filter residue, then washings is retained with after washed with dichloromethane filter residue, then except desolventizing after described filtrate and described washings being merged, retain solid, and use solid described in methyl alcohol and deionized water wash successively, finally use the mixed solution of methyl alcohol and methylene dichloride by described solid recrystallization, obtain described blue light organic phosphorescent electroluminescent materials.
A kind of organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and the negative electrode that stack gradually, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material, and described light emitting guest material is above-mentioned blue light organic phosphorescent electroluminescent materials.
This blue light organic phosphorescent electroluminescent materials is cyclic metal complexes agent structure with 2-(3', 4', 5'-trifluorophenyl) pyrimidine, changes boron for assistant ligand with four (1-pyrazoles).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 blue light organic phosphorescent electroluminescent materials.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the blue light organic phosphorescent electroluminescent materials of an embodiment;
Fig. 2 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 3 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 1;
Fig. 4 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 2;
Fig. 5 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 3;
Fig. 6 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 4;
Fig. 7 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 5;
Fig. 8 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 6;
Fig. 9 is the utilizing emitted light spectrogram of blue light organic phosphorescent electroluminescent materials prepared by embodiment 7.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The blue light organic phosphorescent electroluminescent materials of one embodiment, has following structural formula:
Wherein ,-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20.
General formula-C
nh
2n+1alkyl can be straight chained alkyl or straight chained alkyl.
General formula is-OC
nh
2n+1alkoxyl group can be unbranched alkoxy or branched alkoxy.
In one preferably embodiment, the position of substitution of-R at the 4-of pyrimidine, 5-position.Now, the structural formula of above-mentioned blue light organic phosphorescent electroluminescent materials is:
Concrete, the structural formula of this blue light organic phosphorescent electroluminescent materials can be:
This blue light organic phosphorescent electroluminescent materials can be used as the luminescent material of blue light or white light organic electroluminescent device.
This blue light organic phosphorescent electroluminescent materials is cyclic metal complexes agent structure with 2-(3', 4', 5'-trifluorophenyl) pyrimidine, changes boron for assistant ligand with four (1-pyrazoles).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 blue light organic phosphorescent electroluminescent materials.
In addition, by the introducing of alkyl on pyrimidine ring or alkoxyl group, the electro mass-energy of giving of alkyl or alkoxyl group regulates blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths or oxyalkyl chain are conducive to increasing its solvability in organic solvent in addition, and produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; The introducing that on phenyl ring, the fluorine-based and high field intensity assistant ligand four (1-pyrazoles) of strong electron-withdrawing group group changes boron can improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
The preparation method of above-mentioned blue light organic phosphorescent electroluminescent materials as shown in Figure 1, comprises the steps:
S10, provide Compound D.
The structural formula of Compound D is:
wherein-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20.
In one preferably embodiment, the structural formula of Compound D is:
now, the position of substitution of-R at the 4-of pyrimidine, 5-position.
Compound D directly can be bought from market and obtain.
In present embodiment, Compound D can prepare as follows:
The compounds X and compound Y with following structural formula are provided,
In shielding gas atmosphere, under organic palladium catalyzer, alkali lye and organic solvent existent condition, by compounds X and described compound Y, return stirring 6h ~ 12h at 85 DEG C ~ 100 DEG C carries out Suzuki coupling reaction, obtains Compound D after separation and purification.
Reaction equation is:
Wherein, the mol ratio of compounds X and compound Y can be 1:1 ~ 1.5.
Shielding gas atmosphere can be nitrogen atmosphere or atmosphere of inert gases.
Organic palladium catalyzer can be Pd (PPh
3)
4or Pd (PPh
3)
2cl
2.
The mol ratio of organic palladium catalyzer and compounds X is 2 ~ 5:100.
Alkali lye can be Na
2cO
3or K
2cO
3the aqueous solution.
In alkali lye, the mole number of solute and the mol ratio of compounds X are 1 ~ 3:1.
Organic solvent can be tetrahydrofuran (THF), toluene or DMF.
Compounds X concentration is in organic solvent 0.1mol/L ~ 0.2mol/L.
In present embodiment, the operation obtaining Compound D after separation and purification can be: after mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then use anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retain solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:4 ~ 7 be elutriant, silica gel column chromatography separation carried out to the solid residues obtained, after drying, obtains Compound D.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
S20, under shielding gas atmosphere, the Compound D that step S10 is obtained and IrCl
33H
2o is dissolved in the first solvent, and stirring reaction 22h ~ 25h, obtains compd E after separation and purification at reflux.
The structural formula of compd E is:
Reaction equation is:
In S20, Compound D and IrCl
33H
2the mol ratio of O is 2 ~ 4:1.
Shielding gas atmosphere can be nitrogen atmosphere or atmosphere of inert gases.
First solvent can be the cellosolvo of 3:1 and the mixed solution of water for volume ratio.
The concentration of Compound D in described first solvent is 0.1mol/L ~ 0.2mol/L.
In present embodiment, being operating as of compd E is obtained: mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration after separation and purification, and use filter residue described in distilled water and methanol wash successively, obtain described compd E after drying.
The operation of mixed system remove portion solvent can be realized by rotary evaporation.Except the Specific amounts of desolventizing is determined according to actually operating, generally speaking, there is solid in rotary evaporation to mixed system.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
S30, under above-mentioned shielding gas atmosphere, the compd E obtained by step S20 is dissolved in the second solvent, at room temperature drips the organic solution of Ag organic salt, filters after reacting completely, and removes the solvent in filtrate, obtain solid residues after retaining filtrate.
Shielding gas atmosphere can be nitrogen atmosphere or atmosphere of inert gases.
Second solvent is methylene dichloride, trichloromethane.
In the organic solution of Ag organic salt, Ag organic salt can be trifluoroacetic acid silver, and solvent can be methyl alcohol, and the mol ratio of Ag organic salt and compd E can be 2 ~ 3:1.
The object of S30 adopts silver ions to remove chlorion residual in the compd E obtained in S20, avoids chlorion to affect follow-up reaction.
S40, under above-mentioned shielding gas atmosphere, the solid residues obtained by S30 and compound G are dissolved in the 3rd solvent, and back flow reaction 22h ~ 25h, obtains blue light organic phosphorescent electroluminescent materials after separation and purification.
Shielding gas atmosphere can be nitrogen atmosphere or atmosphere of inert gases.
3rd solvent is acetonitrile.
The concentration of compd E in the 3rd solvent is 0.01mol/L ~ 0.025mol/L.
The structural formula of compound G and blue light organic phosphorescent electroluminescent materials is as follows:
blue light organic phosphorescent electroluminescent materials:
Reaction equation is:
In S40, the mol ratio of compd E and compound G can be 1:2 ~ 3.
In present embodiment, being operating as of blue light organic phosphorescent electroluminescent materials is obtained: mixed system filters after being cooled to room temperature after separation and purification, retain filtrate and filter residue, then washings is retained with after washed with dichloromethane filter residue, then except desolventizing after filtrate and washings being merged, retain solid, and use methyl alcohol and deionized water wash solid successively, finally use the mixed solution of methyl alcohol and methylene dichloride by solid recrystallization, obtain blue light organic phosphorescent electroluminescent materials.
The ratio of the mixed solution of methyl alcohol and methylene dichloride is determined according to actually operating situation.
Except the operation of desolventizing can be realized by rotary evaporation.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
The preparation method of this blue light organic phosphorescent electroluminescent materials is simple to operate, not high to equipment requirements, is easy to promotion and implementation.
The blue light organic phosphorescent electroluminescent materials that the preparation method of this blue light organic phosphorescent electroluminescent materials prepares can be applied to the fields such as organic electroluminescent, organic solar batteries, organic transistor.
Only simply introduce for organic electroluminescence device below.
The organic electroluminescence device 100 of an embodiment as shown in Figure 2, comprises the substrate 101, anode 103, hole injection layer 105, hole transmission layer 107, electronic barrier layer 119, luminescent layer 111, hole blocking layer 113, electron transfer layer 115, electron injection buffer layer 117 and the negative electrode 119 that stack gradually.
The material of substrate 101, anode 103, hole injection layer 105, hole transmission layer 107, electronic barrier layer 119, hole blocking layer 113, electron transfer layer 115, electron injection buffer layer 117 and negative electrode 119 is respectively the common used material of this area.Such as, substrate 101 is common glass substrates, the material of anode 103 is tin indium oxide (ITO), the material of hole injection layer 105 is 4, 4 ', 4 ' '-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), the material of hole transmission layer 107 is N, two (1-the naphthyl)-N of N'-, N '-diphenylbenzidine (NPB), the material of electronic barrier layer 109 is 1, two (9-carbazyl) benzene (mCP) of 3-, the material of hole blocking layer 113 is 2, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene (BCP), the material of electron transfer layer 115 is three (oxine) aluminium (Alq
3), the material of electron injection buffer layer 117 is LiF, the material of negative electrode 119 is metallic aluminium (Al).
The material of luminescent layer 111 comprises light emitting host material and is doped in the light emitting guest material in light emitting host material.Light emitting guest material is blue light organic phosphorescent electroluminescent materials, and light emitting host material is two (9-carbazyl) benzene (mCP) of 1,3-, and the mass ratio of guest materials and material of main part is 7:100.
It is below specific embodiment, the test used in embodiment and apparatus for preparation comprise: high vacuum coating system (scientific instrument development center, Shenyang company limited), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. ocean optics Ocean Optics, Japan's CS-100A colourimeter test brightness of Konica Minolta company and colourity, Japanese Shimadzu RF-5301PC type spectrophotofluorometer is measured and monitored the growth of standing timber material luminescent spectrum.
Embodiment 1
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl) pyrimidine.
Under the protection of nitrogen; by 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.11g (12mmol) 3; 4; 5-trifluoro-benzene boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing the salt of wormwood of 2.76g (20mmol) salt of wormwood subsequently in reaction system.Mixed system is heated to 100 DEG C, and return stirring reaction 6h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:4 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 1.15g after drying, yield is 54.7%.
Structural Identification:
Mass spectrum (MS m/z): 210.0 (M
+);
Ultimate analysis: C10H5F3N2;
Theoretical value: C, 57.15; H, 2.40; F, 27.12; N, 13.33;
Measured value: C, 57.11; H, 2.38; F, 27.22; N, 13.29.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl) pyrimidine.
(2), part be 2-(3', 4', 5'-trifluorophenyl) pyrimidine containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.36g (1mmol) three hydrated iridium trichloride and 0.53g (2.5mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 20mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to pyrimidine, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.36g, yield is 55.7%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.65g (0.5mmol) part; 4'; 5'-trifluorophenyl) pyrimidine be dissolved in 25mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 25mL containing the trifluoroacetic acid silver of 0.24g (1.1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 2h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.48g (1.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, are heated to back flow reaction 24h at 81 DEG C of temperature.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.22g, productive rate is 24.7%.
Structural Identification:
Mass spectrum (MS m/z): 890.2 (M
+);
Ultimate analysis: C32H20BF6IrN12;
Theoretical value: C, 43.20; H, 2.27; B, 1.22; F, 12.81; Ir, 21.61; N, 18.89;
Measured value: C, 43.27; H, 2.16; B, 1.27; F, 12.84; Ir, 21.55; N, 18.91.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl) pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 3, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), blue light organic phosphorescent electroluminescent materials CH under 298K prepared by the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 465nm place, has an acromion at 490nm place simultaneously, thus illustrates that this blue light organic phosphorescent electroluminescent materials can be widely used in the preparation field of organic electroluminescence device.
In addition, 10
-6the CH of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment of M
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=0.44, blue light organic phosphorescent electroluminescent materials prepared by visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine.
Under the protection of nitrogen; by bromo-for 1.73g (10mmol) 2-5-methylpyrimidine, 1.76g (10mmol) 3; 4; 5-trifluoro-benzene boric acid and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing the sodium carbonate of 3.18g (30mmol) sodium carbonate subsequently in reaction system.Mixed system is heated to 90 DEG C, and return stirring reaction 8h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:6 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 1.05g after drying, yield is 46.8%.
Structural Identification:
Mass spectrum (MSm/z): 224.1 (M
+);
Ultimate analysis: C12H8FN3;
Theoretical value: C, 58.93; H, 3.15; F, 25.42; N, 12.50;
Measured value: C, 58.97; H, 3.10; F, 25.46; N, 12.47.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.36g (1mmol) three hydrated iridium trichloride; 0.45g (2mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 20mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-5-methylpyrimidine, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.36g, yield is 53.4%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.67g (0.5mmol) part; 4'; 5'-trifluorophenyl)-5-methylpyrimidine be dissolved in 20mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing the trifluoroacetic acid silver of 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.40g (1.25mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.18g, productive rate is 19.6%.
Structural Identification:
Mass spectrum (MS m/z): 918.2 (M
+);
Ultimate analysis: C34H24BF6IrN12;
Theoretical value: C, 44.50; H, 2.64; B, 1.18; F, 12.42; Ir, 20.95; N, 18.32;
Measured value: C, 44.54; H, 2.66; B, 1.11; F, 12.45; Ir, 20.90; N, 18.35.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl)-5-methylpyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 4, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 462nm place, has an acromion at 497nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.21, blue light organic phosphorescent electroluminescent materials prepared by visible the present embodiment has higher luminous quantum efficiency.
Embodiment 3
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines.
Under the protection of nitrogen; by bromo-for 2.15g (10mmol) 2-5-t-butyl pyrimidines, 2.46g (14mmol) 3; 4; 5-trifluoro-benzene boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing the sodium carbonate of 1.06g (10mmol) sodium carbonate subsequently in reaction system.Mixed system is heated to 85 DEG C, and return stirring reaction 10h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:6 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 1.09g after drying, yield is 40.9%.
Structural Identification:
Mass spectrum (MS m/z): 266.1 (M
+);
Ultimate analysis: C14H13F3N2;
Theoretical value: C, 63.15; H, 4.92; F, 21.41; N, 10.52;
Measured value: C, 63.10; H, 4.98; F, 21.36; N, 10.56.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.36g (1mmol) three hydrated iridium trichloride and 0.80g (3mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 20mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-5-t-butyl pyrimidines, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.30g, yield is 39.6%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.76g (0.5mmol) part; 4'; 5'-trifluorophenyl)-5-t-butyl pyrimidines be dissolved in 25mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 25mL containing the trifluoroacetic acid silver of 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.25g (0.8mmol) four (1-pyrazoles) boronation potassium are dissolved in 25mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.14g, productive rate is 14.0%.
Structural Identification:
Mass spectrum (MS m/z): 1002.3 (M
+);
Ultimate analysis: C40H36BF6IrN12;
Theoretical value: C, 47.96; H, 3.62; B, 1.08; F, 11.38; Ir, 19.19; N, 16.78;
Measured value: C, 47.92; H, 3.67; B, 1.05; F, 11.45; Ir, 19.10; N, 16.81.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl)-5-t-butyl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 5, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 468nm place, has an acromion at 499nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.28.
Embodiment 4
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine.
Under the protection of nitrogen; by 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.19g (7.5mmol) 3,4; 5-trifluoro-benzene boric acid and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing the salt of wormwood of 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Mixed system is heated to 85 DEG C, and return stirring reaction 12h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:5 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 0.66g after drying, yield is 26.9%.
Structural Identification:
Mass spectrum (MS m/z): 490.3 (M
+);
Ultimate analysis: C30H45F3N2;
Theoretical value: C, 73.43; H, 9.24; F, 11.62; N, 5.71;
Measured value: C, 73.40; H, 9.29; F, 11.55; N, 5.76.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.98g (2mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 10mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-4-eicosyl pyrimidine, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.13g, yield is 21.5%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridinecarboxylic) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.48g (0.2mmol) part; 4'; 5'-trifluorophenyl)-4-eicosyl pyrimidine be dissolved in 15mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 15mL containing the trifluoroacetic acid silver of 0.13g (0.6mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.16g (0.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.05g, productive rate is 8.6%.
Structural Identification:
Mass spectrum (MS m/z): 1450.8 (M
+);
Ultimate analysis: C72H100BF6IrN12;
Theoretical value: C, 59.61; H, 6.95; B, 0.75; F, 7.86; Ir, 13.25; N, 11.59;
Measured value: C, 59.66; H, 6.87; B, 0.79; F, 7.82; Ir, 13.29; N, 11.58.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl)-4-eicosyl pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 6, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 477nm place, has an acromion at 508nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.08.
Embodiment 5
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine.
Under the protection of nitrogen; by bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine, 2.11g (12mmol) 3; 4; 5-trifluoro-benzene boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing the salt of wormwood of 2.76g (20mmol) salt of wormwood subsequently in reaction system.Mixed system is heated to 100 DEG C, and return stirring reaction 6h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:6 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 1.08g after drying, yield is 45.0%.
Structural Identification:
Mass spectrum (MS m/z): 240.0 (M
+);
Ultimate analysis: C11H7F3N2O;
Theoretical value: C, 55.01; H, 2.94; F, 23.73; N, 11.66; O, 6.66;
Measured value: C, 55.07; H, 2.88; F, 23.69; N, 11.73; O, 6.63.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.36g (1mmol) three hydrated iridium trichloride; 0.48g (2mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 20mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-5-methoxy pyrimidine, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.33g, yield is 46.7%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluoromethyl phenyl)-5-methoxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.71g (0.5mmol) part; 4'; 5'-trifluorophenyl)-5-methoxy pyrimidine be dissolved in 20m methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing the trifluoroacetic acid silver of 0.24g (1.1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.48g (1.5mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.17g, productive rate is 17.9%.
Structural Identification:
Mass spectrum (MS m/z): 950.2 (M
+);
Ultimate analysis: C34H24BF6IrN12O2;
Theoretical value: C, 43.00; H, 2.55; B, 1.14; F, 12.00; Ir, 20.24; N, 17.70; O, 3.37;
Measured value: C, 43.04; H, 2.48; B, 1.18; F, 12.04; Ir, 20.15; N, 17.77; O, 3.34.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3', 4', 5'-trifluorophenyl))-5-methoxy pyrimidine-N, the C of title complex
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 7, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 463nm place, has an acromion at 494nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.20.
Embodiment 6
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine.
Under the protection of nitrogen; by 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 1.76g (10mmol) 3; 4; 5-trifluoro-benzene boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 40mL DMF, drip the aqueous solution of 20mL containing the sodium carbonate of 1.06g (10mmol) sodium carbonate subsequently in reaction system.Mixed system is heated to 80 DEG C, and return stirring reaction 10h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:7 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 1.39g after drying, yield is 44.8%.
Structural Identification:
Mass spectrum (MS m/z): 310.1 (M
+);
Ultimate analysis: C16H17F3N2O;
Theoretical value: C, 61.93; H, 5.52; F, 18.37; N, 9.03; O, 5.16;
Measured value: C, 61.96; H, 5.46; F, 18.41; N, 9.06; O, 5.11.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.36g (1mmol) three hydrated iridium trichloride and 0.93g (3mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 25mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-4-hexyloxy pyrimidine, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.26g, yield is 30.7%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.85g (0.5mmol) part; 4'; 5'-trifluorophenyl)-4-hexyloxy pyrimidine be dissolved in 20mL trichloromethane containing iridium dichloro dimer; at room temperature drip the methanol solution of 20mL containing the trifluoroacetic acid silver of 0.22g (1mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.32g (1mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.10g, productive rate is 11.5%.
Structural Identification:
Mass spectrum (MS m/z): 1090.3 (M
+);
Ultimate analysis: C44H44BF6IrN12O2;
Theoretical value: C, 48.49; H, 4.07; B, 0.99; F, 10.46; Ir, 17.64; N, 15.42; O, 2.94;
Measured value: C, 48.53; H, 4.10; B, 0.90; F, 10.49; Ir, 17.50; N, 15.48; O, 2.90.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl)-4-hexyloxy pyrimidine-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 8, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 472nm place, has an acromion at 504nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.12.
Embodiment 7
Preparation has the blue light organic phosphorescent electroluminescent materials of following structural formula:
Two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close iridium.
(1), the synthesis of 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines.
Under the protection of nitrogen; by 2.28g (5mmol) 2-bromo-5-eicosyl pyrimidine, 1.32g (7.5mmol) 3; 4; 5-trifluoro-benzene boric acid and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing the sodium carbonate of 1.59g (15mmol) sodium carbonate subsequently in reaction system.Mixed system is heated to 90 DEG C, and return stirring reaction 8h.After mixed system is cooled to room temperature, with dichloromethane extraction, retain organic phase after separatory and wash with water to neutrality, then using anhydrous magnesium sulfate drying, after filtration, retain filtrate, after filtrate decompression distillation, retaining solid residues.Take volume ratio as ethyl acetate and the normal hexane of 1:5 be elutriant, carry out silica gel column chromatography separation to the solid residues obtained, obtain solid 0.58g after drying, yield is 22.9%.
Structural Identification:
Mass spectrum (MS m/z): 506.3 (M
+);
Ultimate analysis: C30H45F3N2O;
Theoretical value: C, 71.11; H, 8.95; F, 11.25; N, 5.53; O, 3.16;
Measured value: C, 71.16; H, 8.87; F, 11.29; N, 5.47; O, 3.21.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines.
(2), part be 2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro.
Under the protection of nitrogen; by 0.18g (0.5mmol) three hydrated iridium trichloride; 1.01g (2mmol) 2-(3'; 4'; 5'-trifluorophenyl) to be dissolved in 10mL volume ratio be in the cellosolvo of 3:1 and the mixed solution of water to-5-eicosane oxygen yl pyrimidines, stirring reaction 24h under reflux state.Mixed system is cooled to remove portion solvent after room temperature, adds distilled water precipitating, retains filter residue after filtration, and use distilled water and methanol wash filter residue successively, after drying solids 0.08g, yield is 12.9%.The dipolymer obtained, without the need to further purification, can directly drop in next step reaction.
(3), two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close the synthesis of iridium.
Under the protection of nitrogen; be 2-(3' by 0.50g (0.2mmol) part; 4'; 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines be dissolved in 15mL methylene dichloride containing iridium dichloro dimer; at room temperature drip the methanol solution of 15mL containing the trifluoroacetic acid silver of 0.13g (0.6mmol) trifluoroacetic acid silver subsequently, dropwise rear stirring reaction 3h.After reaction system is separated by whizzer, the AgCl that throws aside precipitates, and retains supernatant, and then supernatant rotary evaporation is except desolventizing, obtains solid residues.
Under the protection of nitrogen, the solid residues obtained and 0.14g (0.44mmol) four (1-pyrazoles) boronation potassium are dissolved in 20mL acetonitrile, back flow reaction 24h.Mixed system is chilled to room temperature, retains filtrate and filter residue respectively after filtration, and filter residue q. s. methylene chloride washs, and then merges washings and filtrate, and rotary evaporation, except desolventizing, obtains crude product.After crude product uses methyl alcohol, deionized water wash successively, carry out recrystallization with the mixed solution of methyl alcohol and methylene dichloride to crude product and obtain purified product 0.04g, productive rate is 6.7%.
Structural Identification:
Mass spectrum (MS m/z): 1482.8 (M
+);
Ultimate analysis: C72H100BF6IrN12O2;
Theoretical value: C, 58.33; H, 6.80; B, 0.73; F, 7.69; Ir, 12.96; N, 11.34; O, 2.16;
Measured value: C, 58.35; H, 6.75; B, 0.69; F, 7.71; Ir, 12.90; N, 11.30; O, 2.20.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3', 4', 5'-trifluorophenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (four (1-pyrazoles) change boron) close iridium.
As shown in Figure 9, blue light organic phosphorescent electroluminescent materials CH under 298K of preparing of the present embodiment
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 482nm place, has an acromion at 513nm place simultaneously.With the CH of the FIrpic of same concentrations
2cl
2solution is standard (Φ
pL=0.26) Φ of blue light organic phosphorescent electroluminescent materials prepared by the present embodiment, is recorded
pL=0.06.
Embodiment 8
Using the blue light organic phosphorescent electroluminescent materials of embodiment 1 preparation as the preparation of the organic electroluminescence device of light emitting guest material.
It is 200nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as anode, on anode, preparing a layer thickness successively by vacuum evaporation is that the m-MTDATA of 40nm is as hole injection layer, a layer thickness is that the NPB of 20nm is as hole transmission layer, a layer thickness is that the mCP of 10nm is as electronic barrier layer, a layer thickness is the luminescent layer of 30nm, a layer thickness is that the BCP of 10nm is as hole blocking layer, a layer thickness is that the Alq3 of 35nm is as electron transfer layer, thickness is that the LiF of 1nm is as electron injection buffer layer, finally on electron injection buffer layer, vacuum plating techniques of deposition thickness is adopted to be the metal A l of 120nm, as negative electrode.
The material of luminescent layer is the mCP of the blue light organic phosphorescent electroluminescent materials doped with embodiment 1 preparation, and the mass ratio of blue light organic phosphorescent electroluminescent materials prepared by embodiment 1 and mCP is 7:100.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency recording organic electroluminescence device prepared by the present embodiment is 9.6%, and maximum lumen efficiency is 10.5lm/W.
Embodiment 9
Using the blue light organic phosphorescent electroluminescent materials of embodiment 5 preparation as the preparation of the organic electroluminescence device of light emitting guest material.
It is 200nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as anode, on anode, preparing a layer thickness successively by vacuum evaporation is that the m-MTDATA of 40nm is as hole injection layer, a layer thickness is that the NPB of 20nm is as hole transmission layer, a layer thickness is that the mCP of 10nm is as electronic barrier layer, a layer thickness is the luminescent layer of 30nm, a layer thickness is that the BCP of 10nm is as hole blocking layer, a layer thickness is that the Alq3 of 35nm is as electron transfer layer, thickness is that the LiF of 1nm is as electron injection buffer layer, finally on electron injection buffer layer, vacuum plating techniques of deposition thickness is adopted to be the metal A l of 120nm, as negative electrode.
The material of luminescent layer is the mCP of the blue light organic phosphorescent electroluminescent materials doped with embodiment 5 preparation, and the mass ratio of blue light organic phosphorescent electroluminescent materials prepared by embodiment 5 and mCP is 7:100.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency recording organic electroluminescence device prepared by the present embodiment is 5.7%, and maximum lumen efficiency is 6.2lm/W.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a blue light organic phosphorescent electroluminescent materials, is characterized in that, has following structural formula:
Wherein ,-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20.
2. blue light organic phosphorescent electroluminescent materials according to claim 1, is characterized in that, the structural formula of described blue light organic phosphorescent electroluminescent materials is:
3. a preparation method for blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:
The Compound D with following structural formula is provided,
D:
wherein-R is-H, general formula-C
nh
2n+1alkyl or general formula be-OC
nh
2n+1alkoxyl group, n is the integer of 1 ~ 20;
Under shielding gas atmosphere, by described Compound D and IrCl
33H
2o is dissolved in the first solvent, and stirring reaction 22h ~ 25h, obtains compd E after separation and purification at reflux, and the structural formula of described compd E is as follows,
E:
wherein, described Compound D and IrCl
33H
2the mol ratio of O is 2 ~ 4: 1;
Under described shielding gas atmosphere, described compd E is dissolved in the second solvent, at room temperature drips the organic solution of Ag organic salt, filter after reacting completely, remove the solvent in described filtrate after retaining filtrate, obtain solid residues;
Under described shielding gas atmosphere; described solid residues and compound G are dissolved in the 3rd solvent, back flow reaction 22h ~ 25h, obtains blue light organic phosphorescent electroluminescent materials after separation and purification; the structural formula of described compound G and described blue light organic phosphorescent electroluminescent materials is as follows
G:
blue light organic phosphorescent electroluminescent materials:
wherein, the mol ratio of described compd E and described compound G is 1: 2 ~ 3.
4. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 3, is characterized in that, described Compound D prepares as follows,
The compounds X and compound Y with following structural formula are provided,
X：
Y：
In described shielding gas atmosphere; under catalyzer, alkali lye and organic solvent existent condition; by described compounds X and described compound Y, return stirring 6h ~ 12h at 85 DEG C ~ 100 DEG C carries out Suzuki coupling reaction; described Compound D is obtained after separation and purification; wherein, the mol ratio of described compounds X and described compound Y is 1: 1 ~ 1.5.
5. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that,
Described catalyzer is Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, the mol ratio of described catalyzer and described compounds X is 2: 5 ~ 100;
Described alkali lye is Na
2cO
3or K
2cO
3the aqueous solution, in described alkali lye, the mole number of solute and the mol ratio of described compounds X are 1: 3 ~ 1;
Described organic solvent is toluene, tetrahydrofuran (THF) or DMF;
Described compounds X concentration is in organic solvent 0.1mol/L ~ 0.2mol/L.
6. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 3, is characterized in that, the structural formula of described Compound D is:
7. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 3, is characterized in that, described shielding gas atmosphere is nitrogen atmosphere or atmosphere of inert gases;
Described first solvent is volume ratio is the cellosolvo of 3: 1 and the mixed solution of water;
The concentration of described Compound D in described first solvent is 0.1mol/L ~ 0.2mol/L;
Described second solvent is methylene dichloride or trichloromethane;
In the organic solution of described Ag organic salt, Ag organic salt is trifluoroacetic acid silver, and solvent is methyl alcohol, and the mol ratio of described Ag organic salt and described compd E is 2 ~ 3: 1;
Described 3rd solvent is acetonitrile;
The concentration of described compd E in described 3rd solvent is 0.01mol/L ~ 0.025mol/L.
8. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 3, it is characterized in that, being operating as of compd E is obtained: after mixed system remove portion solvent after described separation and purification, add distilled water precipitating, filter residue is retained after filtration, and use distilled water and methanol wash successively, obtain described compd E after drying.
9. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 3, it is characterized in that, being operating as of blue light organic phosphorescent electroluminescent materials is obtained: mixed system filters after being cooled to room temperature after described separation and purification, retain filtrate and filter residue, then washings is retained with after washed with dichloromethane filter residue, then except desolventizing after described filtrate and described washings being merged, retain solid, and use solid described in methyl alcohol and deionized water wash successively, finally use the mixed solution of methyl alcohol and methylene dichloride by described solid recrystallization, obtain described blue light organic phosphorescent electroluminescent materials.
10. an organic electroluminescence device, comprise the substrate, anode, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material, and described light emitting guest material is the blue light organic phosphorescent electroluminescent materials described in claim 1 or 2.
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|---|---|---|---|---|
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| US11674080B2 (en) | 2017-12-14 | 2023-06-13 | Guangzhou Chinaray Optoelectronic Materials Ltd. | Transition metal complex, polymer, mixture, formulation and use thereof |
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