CN104560023A - Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device - Google Patents
Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device Download PDFInfo
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Abstract
The invention provides an organic electroluminescent material, a preparation method of the organic electroluminescent material and an organic electroluminescent device. The organic electroluminescent material has a general formula (P) as shown in the specification, wherein R1 is hydrogen atom, C1-20 linear alkyl, C1-20 branched alkyl, C1-20 linear alkoxy or C1-20 branched alkoxy. According to the organic electroluminescent material, 2-(2',4'-difluoro-3'-cyanophenyl) pyrimidine serving as a cyclometalated ligand and acetylacetone serving as an auxiliary ligand are adopted to synthesize a blue-light organic electroluminescent material iridium complex, and the illuminating color of the material is adjusted through chemical modification performed by introducing alkyl chain on the pyrimidine ring of the cyclometalated ligand, so that phosphorescence emission having blue emission wavelength and high luminescence efficiency can be obtained.
Description
Technical field
The present invention relates to phosphor material field, particularly relate to a kind of electroluminescent organic material.The invention still further relates to the preparation method of this electroluminescent organic 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 (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-ray organic electroluminescent material of over-all properties, 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 Jun Yeob Lee teach problem group of Tan Guo university of Korea S in 2008 reports a kind of novel blue light phosphor material---three (2-(4 ' rolled into a ball by strong electron-withdrawing group in cyano group introducing ring master metal part, 6 '-two fluoro-5 '-cyano-phenyl) pyridine-N, C
2') closing iridium (FCNIr), the maximum emission wavelength of its blue emitting phosphor device PHOLEDs made is blue shifted to 453nm, purity of color CIE
x,yalso be increased to (0.15,0.19).Within 2011, Jun Yeob Lee teach problem group reports the blue emitting phosphor material of cyano-containing in another ring master metal part in succession---two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyridine-N, C
2') (2-pyridinecarboxylic) close iridium (FCNIrpic) excellent properties in blue light and white light parts, by optimised devices structure, the maximum emission wavelength of FCNIrpic blue-light device is blue shifted to 457 ~ 462nm, purity of color CIE
x,yalso be increased to (0.14 ~ 0.18,0.17 ~ 0.25).Facts have proved, in the main part of phosphor material complex of iridium, introduce strong electron-withdrawing substituent-cyano group becomes one of effective ways obtaining novel blue light with high color purity phosphor material.
For different distribution type blue phosphorescent iridium metal complex luminescent material, the assistant ligand that normal employing field intensity is stronger, as 2-pyridinecarboxylic, four (1-pyrazoles) change boron, 5-(2 '-pyridyl)-pyrrotriazole etc.And for being more often applied in green glow or ruddiness iridium metal complex before the methyl ethyl diketone assistant ligand that field intensity is more weak, until the Yunkyoung Ha seminar of Hong Yi university of Korea S in 2012 is at document Journal of Nanoscience and Nanotechnology 2012,12, two (the 2-(2 ' of blue phosphor materials is reported in 668-673,6 '-difluoro pyridine-3 '-Ji)-4-picoline-N, C
2') (methyl ethyl diketone) close iridium [Ir (4-Me-dfpypy)
2(acac)], but its make Nan dian Yao device luminescent properties not good.The Ecole Polytechnique Federale de Lausanne of Switzerland in 2013 combines with Japanese chevron university the J.Mater.Chem.C that publishes an article, 2013,1,1070 – 1075, that mention in literary composition take methyl ethyl diketone as the two (2-(2 ' of blue phosphorescent complex of iridium luminescent material of assistant ligand, 6 '-difluoro pyridine-3 '-Ji)-4-tert .-butylpyridine-N, C
2') (methyl ethyl diketone) close iridium [FK306] and have comparatively outstanding blue light color purity and luminous efficiency, its Nan dian Yao device luminescent properties made is good, maximum work efficiency is more than 30lm/W, maximum current efficiency and the highest external quantum efficiency are respectively 29cd/A and 17%, CIEx, y chromaticity coordinates is (0.16,0.25).Therefore, feeble field strong assistant ligand methyl ethyl diketone can form the good blue phosphorescent luminescent material of luminescent properties with metal iridium coordination together with the strong main part of high field.
The research of people to electroluminescent organic material iridium metal complex is being goed deep into always, but there is bottleneck problem in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Therefore, the blue phosphorescent organic electroluminescent material developing high color purity becomes the megatrend expanding blue light material research field.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of electroluminescent organic material and preparation method thereof and organic electroluminescence device are provided.The invention provides the electroluminescent organic material that one has following general formula (P):
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy.
Further, described R is positioned 4-or the 5-position of its place pyrimidine.
The present invention also provides the preparation method of above-mentioned electroluminescent organic material, and the method comprises the following steps:
E () provides following compd A and compd B:
Described compd A is
Described compd B is
F () is under atmosphere of inert gases, described compd A and described compd B are dissolved in reaction solvent according to the mol ratio of 1:2.5 ~ 1:4, under reflux temperature, carry out ligand exchange reaction, separating-purifying reaction solution, obtain the electroluminescent organic material of following general formula (P):
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy.
In step (b), described reaction solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.The concentration range of described compd A in described mixed solvent is 0.01 ~ 0.0167mol/L.
Further, described compd A adopts following steps to obtain:
C () provides following Compound C and Compound D:
Described Compound C is
described Compound D is three hydrated iridium trichloride;
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy;
D () is under atmosphere of inert gases, described Compound C and described Compound D are added in the cellosolvo aqueous solution according to the mol ratio of 2:1 ~ 4:1, wherein, the volume ratio of cellosolvo and water is 3:1, the concentration range of described Compound D in the described cellosolvo aqueous solution is 0.167 ~ 0.05mol/L, be heated to stirring reaction 24h under reflux state, obtain described compd A.
Further, described Compound C adopts following steps to obtain:
A () provides following compd E and compound F 17-hydroxy-corticosterone:
Described compd E is
described compound F 17-hydroxy-corticosterone is the fluoro-3-cyanophenylboronic acid of 2,4-bis-;
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy;
B () is under atmosphere of inert gases, be that described compd E and the described compound of 1:1 ~ 1:1.5 is dissolved in organic solvent by palladium catalyst, mol ratio, then drip alkaline solution and reheat Suzuki linked reaction 6 ~ 12h to 85 ~ 100 DEG C of temperature, after being cooled to room temperature, separating-purifying, obtains described Compound C.
Further, described palladium catalyst closes palladium for two chlorine two (triphenyl phosphorus) or four (triphenyl phosphorus) close palladium, described alkaline solution is solution of potassium carbonate or sodium carbonate solution, and described organic solvent is toluene solution or DMF solution.
Further, the mol ratio of described palladium catalyst and described compd E is 0.02 ~ 0.05:1; Alkali solute in described alkaline solution and the mol ratio of described compd E are 1 ~ 3:1.
The present invention also proposes a kind of organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that, the material of described luminescent layer is above-mentioned electroluminescent organic material.
Compared with prior art, there is following advantage in electroluminescent organic material of the present invention and preparation method thereof and organic electroluminescence device:
This electroluminescent organic material is cyclic metal complexes agent structure with 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine, take methyl ethyl diketone as assistant ligand.Pyrimidyl on main part is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and cyano group are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl 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; On phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the cyano group of group and assistant ligand methyl ethyl diketone can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
Accompanying drawing explanation
Fig. 1 is the synthetic route of electroluminescent organic material of the present invention.
Fig. 2 is the synthetic route of embodiment 1 electroluminescent organic material.
Fig. 3 is the utilizing emitted light spectrogram of electroluminescent organic material in embodiment 1.
Fig. 4 is the structural representation of organic electroluminescence device in embodiment 8.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Electroluminescent organic material of the present invention has following general formula:
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy; Described R is positioned the 4-of its place pyrimidine, 5-position.
The preparation process of electroluminescent organic material of the present invention (P) is roughly divided into following steps:
(1) make compd E and compound F 17-hydroxy-corticosterone by Suzuki linked reaction synthetic compound C; Wherein, compound F 17-hydroxy-corticosterone is the fluoro-3-cyanophenylboronic acid of 2,4-bis-, and the structural formula of compd E and Compound C is as follows:
Compd E is
compound C is
wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy.
(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) being used as cyclic metal complexes, compd B being used as assistant ligand source, making compd A and compd B react to obtain iridium metal complex, is also electroluminescent organic material (P).The structural formula of compd B is as follows:
Described on total, the invention provides the synthetic route of electroluminescent organic material (P) as shown in Figure 1: i.e. 2-, 4-position and 3-position respectively the phenyl ring of an and cyano group fluorine-based with electrophilic two 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 acetylacetonate sodium reacts obtained target iridium metal complex.
With embodiment, electroluminescent organic material of the present invention and preparation method thereof and organic electroluminescence device are specifically described below:
Embodiment 1
Electroluminescent organic material disclosed in the present embodiment (P) is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine
The building-up reactions formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine is as follows:
Concrete steps are: under nitrogen atmosphere, 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.20g (12mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40ml toluene, drip 20ml subsequently containing 2.76g (20mmol) solution of potassium carbonate in reaction system.Heating, stirring reaction 6h 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.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/6 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.04g, yield is 47.9%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 217.0 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
11h
5f
2n
3; Wherein, theoretical value is: C:60.83, H:2.32, F:17.50, N:19.35; Measured value is: C:60.88, H:2.24, F:17.56, N:19.32.The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine containing the dimeric synthesis of iridium dichloro
Part is the as follows containing iridium dichloro dimeric building-up reactions formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine:
Concrete steps are: under nitrogen atmosphere, 0.36g (1mmol) three hydrated iridium trichloride, 0.54g (2.5mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) to be dissolved in 20ml volume ratio be in the cellosolvo aqueous solution of 3:1 to 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) pyrimidine containing iridium dichloro dimer 0.36g, yield is 54.5%.
(3) title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.66g (0.5mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) being dissolved in 30ml methylene dichloride containing iridium dichloro dimer and 0.15g (1.25mmol) acetylacetonate sodium of pyrimidine, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.48g after steaming and desolventizing vacuum-drying, and yield is 66.2%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 724.1 (M
+); Its ultimate analysis is: C
27h
15f
4irN
6o
2, wherein, its theoretical value is: C:44.81, H:2.09, F:10.50, Ir:26.56, N:11.61, O:4.42; Its measured value is: C:44.78, H:2.15, F:10.46, Ir:26.59, N:11.53, O:4.49.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine-N, C
2') (methyl ethyl diketone) close iridium, is namely electroluminescent organic material (P).
In sum, the synthetic route of the present embodiment electroluminescent organic material as shown in Figure 2.
Consult Fig. 3, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is standardized photoluminescence intensity (NormalizedPL intensity), and the present embodiment electroluminescent organic material is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 466nm place, has an acromion at 491nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.In addition, the present embodiment electroluminescent organic material 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=0.40, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methylpyrimidine-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 1.83g (10mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50ml DMF, drip 25ml subsequently containing 3.18g (30mmol) sodium carbonate solution in reaction system.Be heated to stirring reaction 8h under 90 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.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.92g, yield is 39.8%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 231.1 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
12h
7f
2n
3; Wherein, theoretical value is: C:62.34, H:3.05, F:16.43, N:18.17; Measured value is: C:62.37, H:3.02, F:16.47, N:18.14.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine is as follows:
Concrete steps are: under nitrogen atmosphere, 0.36g (1mmol) three hydrated iridium trichloride, 0.46g (2mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) to be dissolved in 30ml volume ratio be in the cellosolvo aqueous solution of 3:1 to-5-methylpyrimidine, 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methylpyrimidine containing iridium dichloro dimer 0.31g, yield is 45.0%.
(3) title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methylpyrimidine-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methylpyrimidine-N, C
2') (methyl ethyl diketone) to close the reaction formula of the synthesis of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.69g (0.5mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) being dissolved in 40ml trichloromethane containing iridium dichloro dimer and 0.18g (1.5mmol) acetylacetonate sodium of-5-methylpyrimidine, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.45g after steaming and desolventizing vacuum-drying, and yield is 59.9%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 752.1 (M
+); Its ultimate analysis is: C
29h
19f
4irN
6o
2, wherein, the theoretical value of each element percentage composition is: C:46.34, H:2.55, F:10.11, Ir:25.57, N:11.18, O:4.26; Its measured value is: C:46.27, H:2.63, F:10.06, Ir:25.64, N:11.12, O:4.28.The pure products that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methylpyrimidine-N, C
2') (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 465nm place, has an acromion at 490nm 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=0.20.
Embodiment 3
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, the bromo-5-t-butyl pyrimidines of 2.15g (10mmol) 2-, 2.56g (14mmol) 2,4-bis-fluoro-3-cyanophenylboronic acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 35ml DMF, drip 15ml subsequently containing 1.06g (10mmol) sodium carbonate solution in reaction system.Be heated to stirring reaction 10h under 85 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.With volume ratio be 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.90g, yield is 32.9%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 273.1 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
15h
13f
2n
3; Wherein, theoretical value is: C:65.93, H:4.79, F:13.90, N:15.38; Measured value is: C:65.96, H:4.72, F:13.96, N:15.36.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines is as follows:
Concrete steps are: under nitrogen atmosphere, 0.36g (1mmol) three hydrated iridium trichloride, 0.82g (3mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-t-butyl pyrimidines and be dissolved in the 25ml2-ethoxy ethanol aqueous 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 0.17g after drying, yield is 23.5%.
(3) two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.77g (0.5mmol) part be 2-(3 '-cyano group-4 '-fluorophenyl)-5-t-butyl pyrimidines be dissolved in 35ml1 containing iridium dichloro dimer and 0.25g (2mmol) acetylacetonate sodium, in 2-ethylene dichloride, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.44g after steaming and desolventizing vacuum-drying, and yield is 52.6%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 836.2 (M
+); Its ultimate analysis is: C
35h
31f
4irN
6o
2, wherein, the theoretical value of each element percentage composition is: C:50.29, H:3.74, F:9.09, Ir:23.00, N:10.05, O:3.83.Its measured value is: C:50.29, H:3.74, F:9.09, Ir:23.00, N:10.05, O:3.83.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C
2') (2-pyridinecarboxylic) close iridium.
Electroluminescent organic material is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 471nm place, has an acromion at 496nm 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=0.41.
Embodiment 4
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.37g (7.5mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35ml toluene, drip the aqueous solution of 15ml containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 12h 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.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.50g, yield is 20.1%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 497.4 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
31h
45f
2n
3; Wherein, theoretical value is: C:74.81, H:9.11, F:7.63, N:8.44; Measured value is: C:74.86, H:9.04, F:7.67, N:8.43.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine is as follows:
Concrete steps are: under nitrogen atmosphere, 0.18g (0.5mmol) three hydrated iridium trichloride, 0.99g (2mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine is dissolved in the 20ml cellosolvo aqueous 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine containing iridium dichloro dimer 0.10g, yield is 16.4%.
(3) two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.73g (0.3mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-eicosyl pyrimidine be dissolved in 30ml1 containing iridium dichloro dimer and 0.12g (1mmol) acetylacetonate sodium, in 2-ethylene dichloride, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.15g after steaming and desolventizing vacuum-drying, and yield is 19.4%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1284.7 (M
+); Its ultimate analysis is: C
67h
95f
4irN
6o
2, wherein, the theoretical value of each element percentage composition is: C:62.64, H:7.45, F:5.92, Ir:14.96, N:6.54, O:2.49, and its measured value is: C:62.58, H:7.54, F:5.88, Ir:14.99, N:6.47, O:2.54.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C
2') (methyl ethyl diketone) close iridium.
The present embodiment electroluminescent organic material is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 488nm place, has an acromion at 513nm 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=0.13.
Embodiment 5
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methoxy pyrimidine-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, the bromo-5-methoxy pyrimidine of 1.89g (10mmol) 2-, 2.20g (12mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35ml DMF, drip 15ml subsequently containing 2.76g (20mmol) solution of potassium carbonate in reaction system.Be heated to stirring reaction 6h 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.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/7 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.99g, yield is 40.0%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 247.1 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
12h
7f
2n
3o; Wherein, theoretical value is: C:58.30, H:2.85, F:15.37, N:17.00, O:6.47; Measured value is: C:58.34, H:2.78, F:15.43, N:17.03, O:6.42.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine is as follows:
Concrete steps are: under nitrogen atmosphere, 0.36g (1mmol) three hydrated iridium trichloride, 0.49g (2mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) to be dissolved in 20ml volume ratio be in the cellosolvo aqueous solution of 3:1 to-5-methoxy 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-methoxy pyrimidine containing iridium dichloro dimer 0.29g, yield is 40.3%.
(3) two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methoxy pyrimidine-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methoxy pyrimidine-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.72g (0.5mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) being dissolved in 30ml trichloromethane containing iridium dichloro dimer and 0.18g (1.5mmol) acetylacetonate sodium of-5-methoxy pyrimidine, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.43g after steaming and desolventizing vacuum-drying, and yield is 54.8%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 784.1 (M
+); Its ultimate analysis is: C
29h
19f
4irN
6o
4, wherein, the theoretical value of each element percentage composition is: C:44.44, H:2.44, F:9.70, Ir:24.53, N:10.72, O:8.17; Its measured value is: C:44.38, H:2.53, F:9.65, Ir:24.57, N:10.64, O:8.23.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-methoxy pyrimidine-N, C
2') (methyl ethyl diketone) close iridium.′
The present embodiment electroluminescent organic material is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 467nm place, has an acromion at 492nm 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=0.18.
Embodiment 6
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 1.83g (10mmol) 2,4-bis-fluoro-3-cyanophenylboronic acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 40mlDMF, drip the aqueous solution of 20ml containing 1.06g (10mmol) sodium carbonate subsequently in reaction system.Be heated to stirring reaction 10h under 80 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.With volume ratio be 1/10 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.88g, yield is 27.7%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 317.1 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
17h
17f
2n
3o; Wherein, theoretical value is: C:64.34, H:5.40, F:11.97, N:13.24, O:5.04; Measured value is: C:64.37, H:5.33, F:11.95, N:13.33, O:5.02.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine is as follows:
Concrete steps are: under nitrogen atmosphere, 0.36g (1mmol) three hydrated iridium trichloride and 0.95g (3mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine is dissolved in the 25ml2-ethoxy ethanol aqueous 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer 0.24g, yield is 27.9%.
(3) two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.69g (0.4mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl) being dissolved in 40ml trichloromethane containing iridium dichloro dimer and 0.15g (1.2mmol) acetylacetonate sodium of-4-hexyloxy pyrimidine, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains product 0.32g after steaming and desolventizing vacuum-drying, and yield is 43.3%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 924.3 (M
+); Its ultimate analysis is: C
39h
39f
4irN
6o
4, wherein, the theoretical value of each element percentage composition is: C:50.70, H:4.25, F8.22, Ir:20.80, N:9.10, O:6.93; Its measured value is: C:50.66, H:4.31, F:8.17, Ir:20.85, N:9.13, O:6.88.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C
2') (methyl ethyl diketone) close iridium.
The present embodiment electroluminescent organic material 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=0.15.
Embodiment 7
Electroluminescent organic material disclosed in the present embodiment is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines
The reaction formula of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines synthesis is as follows:
Concrete steps are: under nitrogen atmosphere, 2.28g (5mmol) 2-bromo-5-eicosyl pyrimidine, 1.37g (7.5mmol) 2, the fluoro-3-cyanophenylboronic acid of 4-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35ml toluene, drip 15ml subsequently containing 1.59g (15mmol) sodium carbonate solution in reaction system.Be heated to stirring reaction 8h under 90 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.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.50g, yield is 19.5%.
Carry out Structural Identification to described solid to obtain: mass spectrum (MS m/z): 513.3 (M
+).Carry out ultimate analysis to described solid to obtain: its molecular formula is C
31h
45f
2n
3o; Wherein, theoretical value is: C:72.48, H:8.83, F:7.40, N:8.18, O:3.11; Measured value is: C:72.44, H:8.87, F:7.43, N:8.14, O:3.12.
The solid that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines.
(2) part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro
Part is that the reaction formula containing the synthesis of iridium dichloro dimer of 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines is as follows:
Concrete steps are: under nitrogen atmosphere, 0.18g (0.5mmol) three hydrated iridium trichloride, 1.03g (2mmol) 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines is dissolved in the 30ml2-ethoxy ethanol aqueous 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, after drying part be 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer 0.09g, yield is 14.4%.
(3) two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (methyl ethyl diketone) close the synthesis of iridium
Two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (methyl ethyl diketone) to close the building-up reactions formula of iridium as follows:
Concrete steps are: under nitrogen atmosphere, 0.75g (0.3mmol) part is 2-(2 ', 4 '-two fluoro-3 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines be dissolved in 30ml1 containing iridium dichloro dimer and 0.15g (1.2mmol) acetylacetonate sodium, in 2-ethylene dichloride, be heated to reflux state stirring reaction 24h.After being chilled to room temperature, remove solvent under reduced pressure, with a small amount of methylene dichloride again dissolution residual substance, distilled water extraction mixed solution is to remove unreacted acetylacetonate sodium.Organic phase anhydrous magnesium sulfate drying, filters, and filtrate decompression obtains pure products 0.14g after steaming and desolventizing vacuum-drying, and yield is 17.7%.
Structural Identification is carried out to gained pure products: its mass spectrum (MS m/z) is: 1316.7 (M
+); Its ultimate analysis is: C
67h
95f
4irN
6o
4, wherein, the theoretical value of each element percentage composition is: C:61.12, H:7.27, F:5.77, Ir:14.60, N:6.38, O:4.86; Its measured value is: C:61.06, H:7.35, F:5.74, Ir:14.65, N:6.33, O:4.87.The pure products that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (methyl ethyl diketone) close iridium.
The present embodiment electroluminescent organic material is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 492nm place, has an acromion at 518nm 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=0.09.
Embodiment 8
With the electroluminescent organic material that embodiment 1 is obtained two (2-(4 ', 6 '-two fluoro-5 '-cyano group) pyrimidine-N, C
2') (methyl ethyl diketone) close iridium as luminescent layer doping object organic electroluminescence device, structure as shown in Figure 4:
This organic electroluminescence device comprise stack gradually substrate, anode layer 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, buffer layer 307 and cathode layer 308.Wherein:
Substrate adopts glass (Glass), and the material of anode layer 301 is that ITO, ITO are prepared in glass surface, is called for short ito glass together with glass.Certainly, the material of anode layer 301 also can be FTO, AZO, IZO.Be preferably the ITO(tin indium oxide that square resistance is 10-20 Ω), thickness is 150nm;
The material of hole injection layer 302 is DNTPD(N, N '-phenylbenzene-N, N '-bis-[4-(N "-phenyl-N "-Tolylamino) phenyl]-biphenyl-4,4 '-diamines), thickness 60nm;
The material of hole transmission layer 303 is NPB(N, N '-bis-(1-naphthyl)-N, N '-diphenylbenzidine), thickness 30nm;
The material of luminescent layer 304 is the electroluminescent organic material two (2-(4 ', 6 '-two fluoro-5 '-cyano group) pyrimidine-N, the C that prepare doped with 7wt embodiment 1
2') (methyl ethyl diketone) close the mCP (1,3-two (9-carbazyl) benzene) of iridium, thickness 30nm;
The material of hole blocking layer 305 is BCP(2,9-dimethyl-4,7-phenylbenzene-phenanthrolene), thickness 5nm;
The material of electron transfer layer 306 is Alq
3(three (oxine) aluminium), thickness is 20nm;
The material of buffer layer 307 is LiF, thickness 1nm;
The material of cathode layer 308 is Al layer, thickness 200nm.
The structure of this organic electroluminescence device is: ITO (150nm)/DNTPD (60nm)/NPB (30nm)/SiCa:7wt%Ir title complex (30nm)/BCP (5nm)/Alq
3(20nm)/LiF (1nm)/Al (200nm); Wherein, brace "/" represents laminate structure, and colon ": " represents doping.
The preparation technology of this organic electroluminescence device is as follows:
It is 150nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω is as transparent anode 301, on anode 301, the DNTPD(N that a layer thickness is 60nm is prepared successively by vacuum evaporation, N '-phenylbenzene-N, N '-bis-[4-(N "-phenyl-N "-Tolylamino) phenyl]-biphenyl-4, 4 '-diamines) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB (N of 30nm, N '-bis-(1-naphthyl)-N, N '-diphenylbenzidine) hole mobile material is the two (2-(4 ' prepared doped with 7wt% embodiment 1 of 30nm as hole transmission layer 303 and a layer thickness, 6 '-two fluoro-5 '-cyano group) pyrimidine-N, C
2') (methyl ethyl diketone) close the mCP (1 of iridium, two (9-carbazyl) benzene of 3-) as luminescent layer 304, on this luminescent layer 304, vacuum evaporation a layer thickness is successively the BCP (2 of 5nm again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) material is the Alq of 20nm as hole blocking layer 305, thickness
3(three (oxine) aluminium) as electron transfer layer 306, thickness be the LiF of 1nm as electron injection buffer layer 307, finally adopt vacuum plating techniques of deposition thickness to be the metal A l of 200nm on the buffer layer, as the negative electrode 308 of device.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, record the maximum emission wavelength of organic electroluminescence device at 468nm place, an acromion is had at 494nm place, the maximum external quantum efficiency of device is 8.3%, and maximum lumen efficiency is 7.3lm/W.
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. there is the electroluminescent organic material of following general formula (P):
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy.
2. electroluminescent organic material as claimed in claim 1, it is characterized in that, described R is positioned 4-or the 5-position of its place pyrimidine.
3. a preparation method for electroluminescent organic material, is characterized in that, the method comprises the following steps:
E () provides following compd A and compd B:
Described compd A is
described compd B is
F () is under atmosphere of inert gases, described compd A and described compd B are dissolved in reaction solvent according to the mol ratio of 1:2.5 ~ 1:4, under reflux temperature, carry out ligand exchange reaction, separating-purifying reaction solution, obtain the electroluminescent organic material of following general formula (P):
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy.
4. preparation method according to claim 3, is characterized in that, in step (f), described reaction solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
5. preparation method according to claim 3, is characterized in that, in step (f), the concentration range of described compd A in described mixed solvent is 0.01 ~ 0.0167mol/L.
6. preparation method according to claim 3, is characterized in that, described compd A adopts following steps to obtain:
C () provides following Compound C and Compound D:
Described Compound C is
described Compound D is three hydrated iridium trichloride;
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy;
D () is under atmosphere of inert gases, described Compound C and described Compound D are added in the cellosolvo aqueous solution according to the mol ratio of 2:1 ~ 4:1, wherein, the volume ratio of cellosolvo and water is 3:1, the concentration range of described Compound D in the described cellosolvo aqueous solution is 0.167 ~ 0.05mol/L, be heated to stirring reaction 24h under reflux state, obtain described compd A.
7. preparation method according to claim 6, is characterized in that, described Compound C adopts following steps to obtain:
A () provides following compd E and compound F 17-hydroxy-corticosterone:
Described compd E is
described compound F 17-hydroxy-corticosterone is the fluoro-3-cyanophenylboronic acid of 2,4-bis-;
Wherein, R is hydrogen atom, C
1 ~ 20straight chained alkyl, C
1 ~ 20branched-chain alkyl, C
1 ~ 20unbranched alkoxy or C
1 ~ 20branched alkoxy;
B () is under atmosphere of inert gases, be that described compd E and the described compound F 17-hydroxy-corticosterone of 1:1 ~ 1:1.5 is dissolved in organic solvent by palladium catalyst, mol ratio, then drip alkaline solution and reheat Suzuki linked reaction 6 ~ 12h to 85 ~ 100 DEG C of temperature, after being cooled to room temperature, separating-purifying, obtains described Compound C.
8. want the preparation method described in 7 according to right, it is characterized in that, described palladium catalyst closes palladium for two chlorine two (triphenyl phosphorus) or four (triphenyl phosphorus) close palladium, described alkaline solution is solution of potassium carbonate or sodium carbonate solution, described organic solvent is toluene solution or DMF solution.
9. preparation method according to claim 7, is characterized in that, the mol ratio of described palladium catalyst and described compd E is 0.02 ~ 0.05:1; Alkali solute in described alkaline solution and the mol ratio of described compd E are 1 ~ 3:1.
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 the electroluminescent organic material described in claim 1 or 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3945125A1 (en) * | 2020-07-28 | 2022-02-02 | Novaled GmbH | Compound of formula (i), a semiconductor material comprising at least one compound of formula (i), an semiconductor layer comprising at least one compound of formula (i) and an electronic device comprising at least one compound of formula (i) |
| WO2022023278A1 (en) * | 2020-07-28 | 2022-02-03 | Novaled Gmbh | Metal complexes of 4-(2,4-dioxopent-3-yl)-2,3,5,6-tetrafluorobenzonitrile and similar ligands as semiconductor materials for use in electronic devices |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3945125A1 (en) * | 2020-07-28 | 2022-02-02 | Novaled GmbH | Compound of formula (i), a semiconductor material comprising at least one compound of formula (i), an semiconductor layer comprising at least one compound of formula (i) and an electronic device comprising at least one compound of formula (i) |
| WO2022023278A1 (en) * | 2020-07-28 | 2022-02-03 | Novaled Gmbh | Metal complexes of 4-(2,4-dioxopent-3-yl)-2,3,5,6-tetrafluorobenzonitrile and similar ligands as semiconductor materials for use in electronic devices |
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