CN103172680A - Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device - Google Patents
Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device Download PDFInfo
- Publication number
- CN103172680A CN103172680A CN2011104305804A CN201110430580A CN103172680A CN 103172680 A CN103172680 A CN 103172680A CN 2011104305804 A CN2011104305804 A CN 2011104305804A CN 201110430580 A CN201110430580 A CN 201110430580A CN 103172680 A CN103172680 A CN 103172680A
- Authority
- CN
- China
- Prior art keywords
- organic electroluminescence
- iridium
- phosphor material
- compd
- look phosphor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *c1cc(Br=C)ncc1 Chemical compound *c1cc(Br=C)ncc1 0.000 description 2
- CAHKHUOPOJIFIJ-UHFFFAOYSA-N Cc1ccnc(-c(ccc(F)n2)c2F)c1 Chemical compound Cc1ccnc(-c(ccc(F)n2)c2F)c1 CAHKHUOPOJIFIJ-UHFFFAOYSA-N 0.000 description 1
- MBTGBRYMJKYYOE-UHFFFAOYSA-N Fc1cccc(F)n1 Chemical compound Fc1cccc(F)n1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the photoelectric material field, and discloses an iridium-containing organic electroluminescence blue light phosphorescence material, a preparation method and an organic electroluminescent device; the iridium-containing organic electroluminescence material comprises a following structural formula: in the formula, R is C1-C4 alkyl. A molecular structure of the iridium-containing organic electroluminescence blue light phosphorescence material contains a dipyridine ligand, an alkoxyl group and a fluorine group; so that the carrier injection and transmission capability of the polymer can be enhanced, and the iridium-containing organic electroluminescence material has high internal quantum efficiency and electroluminescent efficiency; in addition, the iridium-containing organic electroluminescence material employs a strong field ligand tetra pyrazoles boron potassium as an auxiliary ligand, thereby the luminescence spectrum enables effective blue shift, and the luminescence efficiency of blue light phosphorescence can be greatly enhanced.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of iridium organic electroluminescence look phosphor material and preparation method thereof that turns blue that contains.The invention still further relates to a kind of luminescent layer and include the organic electroluminescence device that this contains the polymerization of iridium organic electroluminescent.
Background technology
Organic electroluminescent (EL) refers to organic materials under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Early stage too high due to the driving voltage of made device, that luminous efficiency is low etc. is former thereby make the research to organic electroluminescent stay cool.Until 1987, the people such as the Tang of Kodak have invented with oxine aluminium (Alq in document and patent US4356429
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how to take full advantage of all the other phosphorescence of 75% and realizes that higher luminous efficiency has become the hot research direction in this field after this.1997, Forrest etc. found the electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material is broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, good stability due to its compound, reaction conditions is gentle in building-up process, and have very high electroluminescent properties, accounting for dominant position always in research process subsequently.And in order to make device obtain full-color demonstration, generally must obtain simultaneously ruddiness, green glow and the blue light material of excellent performance.Compare with green light material with ruddiness, the development of blue light material lags behind comparatively speaking, and the efficient that improves blue light material and purity of color have just become the breakthrough point of people's researchs.Up to now, two [2-(2,4 difluorobenzene base) pyridine-N, C
2] (pyridine carboxylic acid) to close iridium (FIrpic) be that the document patent report gets one of Ir (III) a metal-organic complex blue phosphorescent electroluminescent material at most.Although people have carried out various optimizations to FIrpic class OLED structure, device performance also is greatly improved, but the weakness of FIrpic maximum is exactly the blue light of being sent out is sky blue, blue light color purity is not good enough, the CIE of each OLED device of making changes between (0.13～0.17,0.29～0.39).Therefore, develop highly purified blue phosphorescent organic electroluminescent material and become a megatrend of expanding the blue light material research field.
Summary of the invention
The object of the present invention is to provide a kind of can send blue emitting phosphor contain the iridium organic electroluminescence look phosphor material that turns blue.
The iridium organic electroluminescence look phosphor material that turns blue that contains provided by the invention has following general structural formula:
In formula, R is C
1～C
4Alkyl.
Another object of the present invention is to provide above-mentioned the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains, its step is as follows:
In S1, oxygen-free environment, with general structure be
Compd A and three hydration iridous chlorides added in 3: 1～5: 1 in the first organic solvent (as, cellosolvo) according to mol ratio, after dissolving, be warming up to the first organic solvent reflux state, reaction generating structure formula is
Two endo compound B; Wherein, R is C
1～C
4Alkyl;
In S2, oxygen-free environment, with described two endo compound B and structural formula be
Four pyrazoles boronation potassium according to mol ratio added in 1: 2.5～1: 3.5 the second organic solvent (as, 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF)) in, then add in the second organic solvent the first catalyzer (as, the mol ratio sodium methylate of 5: 1 and silver trifluoromethanesulfonate), stirring is warming up to the second organic solvent reflux state, and the generating structure formula is
The described iridium organic electroluminescence look phosphor material that turns blue that contains.
The above-mentioned iridium organic electroluminescence that contains turns blue in preparation method's the step S1 of look phosphor material, and described compd A is to adopt following step to make:
S11, in the anhydrous and oxygen-free environment, with structural formula be
Compound D and diisopropylamine lithium add at 1.2: 1 in tetrahydrofuran (THF) (THF) solution according to mol ratio, react under-78 ℃; Then add trimethyl borate toward reaction mixture, continue reaction at normal temperatures, the generating structure formula as
Compd E;
S12, with described compd E and general structure be
Compound F 17-hydroxy-corticosterone added in 1.5: 1～2: 1 according to mol ratio and contain catalyzer (as, K
2CO
3The aqueous solution and Pd (PPh
3)
4Mixture, described K
2CO
3Molar weight be 10 times of molar weight of described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4Molar weight be described compound F 17-hydroxy-corticosterone molar weight 0.5%) the 3rd organic solvent (as, tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO)), be warming up under the 3rd organic solvent reflux state and carry out the Suzuki linked reaction, generate described compd A; Wherein, in described compound F 17-hydroxy-corticosterone, R is C
1～C
4Alkyl.
Wherein, also comprise purification step to compd E in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; Then be that the pH value of HCl aqueous solution conditioned reaction mixed solution of 3N is to neutral with equivalent concentration; Then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying.
Wherein, also comprise the step that compd A is purified in described step S12:
After adding appropriate distilled water in the reaction mixture that contains described compd A, then repeatedly extract with ethyl acetate, merge organic phase; Secondly use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Use at last ethyl acetate and normal hexane mixed solution to make eluent and the filtrate residue is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
Another goal of the invention of the present invention is to provide a kind of organic electroluminescence device, and the luminescent layer of this organic electroluminescence device comprises and contain the iridium organic electroluminescence look phosphor material that turns blue, and this contains the iridium organic electroluminescence look phosphor material that turns blue and has following structural formula:
The iridium organic electroluminescence look phosphor material that turns blue that contains provided by the invention contains bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it have higher internal quantum efficiency and electroluminescent efficiency; In addition, contain the iridium organic electroluminescence and turn blue that to adopt high field part 2-pyridine carboxylic acid be assistant ligand to the look phosphor material, make the effective blue shift of its luminescent spectrum, greatly increased the luminous efficiency of blue emitting phosphor.
Description of drawings
Fig. 1 contains the iridium organic electroluminescence look phosphor material ((dfpyMepy) that turns blue in embodiment 1
2Ir6) CH
2Cl
2The PL spectrogram of solution under 298K;
Fig. 2 is the structural representation of organic electroluminescence device in embodiment 5.
Embodiment
The iridium organic electroluminescence look phosphor material that turns blue that contains provided by the invention, iridium (Ir) a metal-organic complex is a kind of phosphorescent light-emitting materials with shorter phosphorescent lifetime (1～14 μ s); Contain the iridium organic electroluminescence look phosphor material that turns blue, have molecular formula (dfpyMepy)
2Ir6; Wherein, dfpy represents on cyclic metal complexes one 2, two fluorine-based substituent pyridine rings of 6-bit strip; Rpy represents the pyridine ring of another 4-bit strip alkoxy substituent on cyclic metal complexes; Two pyridine rings connect into dipyridyl with 2-, 3-position respectively; Assistant ligand four pyrazoles boron in 6 expression title complexs.The described iridium organic electroluminescence look phosphor material that turns blue that contains has following structural formula:
In formula, " 2 " represent that this general structure contains two structures and is
Ligand; Wherein, R is C
1～C
4Alkyl.
The iridium organic electroluminescence look phosphor material that turns blue that contains provided by the invention contains bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it have higher internal quantum efficiency and electroluminescent efficiency; In addition, contain the iridium organic electroluminescence and turn blue that to adopt high field part four pyrazoles boronation potassium be assistant ligand to the look phosphor material, make the effective blue shift of its luminescent spectrum, greatly increased the luminous efficiency of blue emitting phosphor.
Above-mentioned the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains, its step is as follows:
In S1, oxygen-free environment (being consisted of by rare gas element, as nitrogen atmosphere or argon gas atmosphere), with structural formula be
Compd A and three hydration iridous chloride (lrCl
33H
2O) according to mol ratio 3: 1～5: 1 (preferred 4: 1) add the first organic solvent (as, cellosolvo) in, after dissolving, be warming up to 135 ℃ (namely, the boiling temperature of cellosolvo, the reflux temperature of cellosolvo namely) reflux state, reaction generating structure general formula is
Two endo compound B ((dfpyORpy)
2Ir (μ-Cl)-(dfpyORpy)
2); Wherein, R is C
1～C
4Alkyl; This reaction formula is as follows:
In S2, oxygen-free environment (being consisted of by rare gas element, as nitrogen atmosphere or argon gas atmosphere), with described two endo compound B and structural formula be
Four pyrazoles boronation potassium (KB (pz)
4) according to mol ratio 1: 2.5～1: 3.5 (preferred 1: 3) add the second organic solvent (as, 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF) (THF)) in, the co-catalyst effect that forms at the mol ratio sodium methylate of 5: 1 and silver trifluoromethanesulfonate (AgOTf), (this temperature range is the boiling temperature scope of the second organic solvent to be warming up to 61 ℃～135 ℃, the reflow temperature range of the second organic solvent namely) carry out ligand exchange reaction, the generating structure formula under reflux state
For contain iridium organic electroluminescence turn blue look phosphor material, i.e. (dfpyRpy)
2Ir6; Wherein, the second different organic solvents, its reflux temperature is different, as, 1,2-ethylene dichloride, trichloromethane, cellosolvo and the tetrahydrofuran (THF) reflux temperature of correspondence respectively are 83.5 ℃, 61.5 ℃, 135 ℃ and 63.5 ℃; This reaction formula is as follows:
The above-mentioned iridium organic electroluminescence that contains turns blue in look phosphor material preparation method's step S1, and described compd A is to adopt following step to make:
S11, in anhydrous and oxygen-free environment (being consisted of by rare gas element, as nitrogen atmosphere or argon gas atmosphere), with structural formula be
Compound D (namely 2, the 6-difluoro pyridine) and diisopropylamine lithium (be called for short LDA) add at 1.2: 1 in tetrahydrofuran (THF) (THF) solution according to mol ratio, react under-78 ℃, the reaction times is probably 0.5～2h, make 2,6-difluoro pyridine base-3-lithium; Then add the trimethyl borate (B (OMe) of 12.5mmol toward reaction mixture
3), 2,6-difluoro pyridine base-3-lithium and trimethyl borate (B (OMe)
3) continue reaction at normal temperatures, the generating structure formula as
Compd E (namely 2,6-two fluoro-3-boric acid pyridines); Reaction formula is as follows:
S12, with described compd E and general structure be
Compound F 17-hydroxy-corticosterone (4-alkyl-2-bromopyridine) add according to mol ratio 1.5: 1～2: 1 (preferred 1.6: 1) and contain catalyzer (as, K
2CO
3The aqueous solution and Pd (PPh
3)
4Mixture, described K
2CO
3Molar weight be 10 times of molar weight of described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4Molar weight be described compound F 17-hydroxy-corticosterone molar weight 0.5%) the 3rd organic solvent (as, tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO)), be warming up to 70～100 ℃ of (reflow temperature range of the 3rd organic solvent namely, because each self-corresponding boiling temperature of tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO) is respectively 63.5 ℃, 101.5 ℃, 110.8 ℃, 189 ℃, these the 3rd organic solvents are with after water mixes, and its reflux temperature can change to some extent; Boiling temperature is during lower than the boiling temperature of water, and its reflux temperature is probably 70 ℃, when the boiling point of solvent temperature during higher than water pretty young woman boiling temperature, reflux temperature is the boiling temperature of water, namely 100 ℃) under reflux state, carry out the Suzuki linked reaction, generate described compd A; Wherein, in compound F 17-hydroxy-corticosterone, R is C
1～C
4Alkyl; Reaction formula is as follows:
Wherein, also comprise the step that compd E is purified in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; Then be that the pH value of HCl aqueous solution conditioned reaction mixed solution of 3N is to neutral with equivalent concentration; Then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying.
Wherein, also comprise the step that compd A is purified in described step S12:
After adding appropriate distilled water in the reaction mixture that contains described compd A, then repeatedly extract with ethyl acetate, merge organic phase; Secondly use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Use at last ethyl acetate and normal hexane to mix the mixed solution that forms and make eluent and the filtrate residue is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
Turn blue in the preparation method of look phosphor material at the above-mentioned iridium organic electroluminescence that contains, in order to obtain more highly purified compd B, the compd B that needs step S1 is made carries out purification processes, and its treating processes is as follows:
S11, reaction mixture is carried out concentrating under reduced pressure process;
S12, take methylene dichloride as elutriant, concentrated solution is carried out silica gel column chromatography and separate, obtain the compd B of purifying.
In like manner, turn blue in the preparation method of look phosphor material at the above-mentioned iridium organic electroluminescence that contains, in order to obtain the more highly purified iridium organic electroluminescence look phosphor material that turns blue that contains, need the iridium organic electroluminescence look phosphor material that turns blue that contains that step S2 makes is carried out purification processes, its treating processes is as follows:
S21, suitable concentrated the turn blue reaction mixture of look phosphor material of iridium organic electroluminescence that contains, after namely removing a part of solvent, the appropriate distilled water of impouring is to separate out solid;
Crude product is collected in S22, filtration, uses successively normal hexane, ether supersound washing;
S23, separate as elutriant carries out silica gel column chromatography to it with the mixed solution of methylene dichloride take normal hexane, what obtain purifying contains the iridium organic electroluminescence look phosphor material that turns blue.
Contain the material of main part that the iridium organic electroluminescence turns blue in look phosphor material and organic electroluminescence device luminescent layer and have consistency preferably, can be used as the organic electroluminescence device that doping object in luminescent layer is widely used in the blue or white phosphorescence of preparation; This contains the iridium organic electroluminescence look phosphor material that turns blue and has following general structure:
In formula, R is C
1～C
4Alkyl.
The iridium organic electroluminescence look phosphor material that turns blue that contains provided by the invention contains bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it have higher internal quantum efficiency and electroluminescent efficiency; In addition, contain the iridium organic electroluminescence and turn blue that to adopt high field part four pyrazoles boronation potassium be assistant ligand to the look phosphor material, make the effective blue shift of its luminescent spectrum, greatly increased the luminous efficiency of blue emitting phosphor.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The present embodiment contain the iridium organic electroluminescence look phosphor material that turns blue, namely title complex two (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium [(dfpyMepy)
2Ir6], wherein R is methyl:
Title complex two (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium [(dfpyMepy)
2Ir6] preparation technology as follows:
Synthesizing of (1) 2,6-, two fluoro-3-boric acid pyridines
Under nitrogen protection, the N-Lithiodiisopropylamide of 7.5mL (12mmol) 1.6M and 0.91mL (10mmol) 2, the 6-difluoro pyridine adds in the 40mL tetrahydrofuran solution, keeps-78 ℃ of temperature stirring reaction 1h.The question response system is warming up to room temperature after adding 1.40mL (12.5mmol) trimethyl borate naturally, continues stirring reaction 1h.It is the NaOH aqueous solution termination reaction of 5wt% that reaction mixture slowly adds 20mL quality percentage composition, and after stirring 10min, dropwise adding appropriate equivalent concentration is that the HCl aqueous solution adjust pH of 3N is to neutral.Ethyl acetate repeatedly extracts, and merges organic phase, and rotation is steamed and desolventized, and gets white solid thing 1.43g, and yield is 90%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.45(d，1H)，6.94(d，1H)，5.33(s，2H).
(2) 2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl [dfpyMepy] synthetic
Under nitrogen protection, (0.45mL, 4.00mmol) 2-bromo-4-picoline, (0.76g, 4.80mmol) 2,6-two fluoro-3-boric acid pyridines, (0.28g, 0.24mmol) Pd (PPh
3)
4After being dissolved in 25mL THF, adding the 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to 70 ℃ of reflux states, stirring reaction 18h.
After question response stops, after naturally being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=as elutriant carry out silica gel column chromatography separate at 1: 3, get colorless solid product 0.53g, yield is 64.3%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.58(d，1H)，8.43(d，1H)，7.70(s，1H)，7.62(d，1H)，6.92(d，1H)，2.61(s，3H).
(3) two endo compounds (dfpyMepy)
2Ir (the Ir (dfpyMepy) of μ-Cl)
2Synthetic
Under nitrogen protection, 1.65g (8mmol) 2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.91g, yield is 71.3%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.66(d，4H)，7.57(s，4H)，6.74(s，4H)，2.70(s，12H).
(4) title complex two (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium [(dfpyMepy)
2Ir6] synthetic
Under nitrogen protection, the methanol solution that 60mL contains 0.81g (3.15mmol) AgOTf slowly is added drop-wise to 60mL and contains 1.91g (1.5mmol) two endo compounds (dfpyMepy)
2Ir (the Ir (dfpyMepy) of μ-Cl)
2The 1.2-dichloromethane solution in, stirring reaction 2h under room temperature.The whizzer separation gets settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 1.43g (4.5mmol) KBpz
4Be dissolved in the 50mL acetonitrile 83.5 ℃ of back flow reaction 24h.
After question response stops, being chilled to room temperature, filtering, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and gets crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization gets pure products 0.54g, and productive rate is 20.4%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.78(d，1H)，8.71(d，1H)，7.96(d，2H)，7.83(d，2H)，7.73(d，2H)，7.60(d，1H)，7.58(d，1H)，7.51(s，1H)，7.48(s，1H)，7.43(d，2H)，7.15(s，1H)，7.10(s，1H)，6.58(m，2H)，6.51(m，2H)，2.90(s，6H).
Fig. 1 contains the iridium organic electroluminescence to turn blue the look phosphor material [(dfpyMepy) in embodiment 1
2Ir6] CH
2Cl
2The PL spectrogram of solution under 298K; Wherein, test condition is: under 298K, volumetric molar concentration is～10
-5The CH of M
2Cl
2Solution carries out; As shown in Figure 1, λ
max PLDuring=431nm, at the 451nm place, one acromion is arranged.
Embodiment 2
The present embodiment contain the iridium organic electroluminescence look phosphor material that turns blue, namely title complex two (2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium, wherein R is ethyl:
Title complex two (2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) to close the preparation technology of iridium as follows:
(1) 2,6-, two fluoro-3-boric acid pyridines synthetic identical with step (1) in case study on implementation 1;
(2) 2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl synthetic
Under argon shield, (0.48mL, 4.00mmol) 2-bromo-4-ethylpyridine, (0.76g, 4.80mmol) 2,6-two fluoro-3-boric acid pyridines, (0.28g, 0.24mmol) Pd (PPh
3)
4After being dissolved in the 25mL dioxane, adding the 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to 100 ℃ of reflux states, stirring reaction 18h.
After question response stops, after naturally being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=as elutriant carry out silica gel column chromatography separate at 1: 4, get colorless solid product 0.57g, yield is 60.8%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.60(d，1H)，8.45(d，1H)，7.71(s，1H)，7.64(d，1H)，6.94(d，1H)，3.46(m，2H)，1.78(m，3H).
Synthesizing of (3) two endo compounds
Under argon shield, 1.78g (8mmol) 2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.
After the band reaction stops, after naturally being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.90g, yield is 67.6%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.81(d，4H)，7.67(d，4H)，7.56(s，4H)，6.75(s，4H)，3.50(m，8H)，1.82(m，12H).
(4) title complex two (2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close the synthetic of iridium
Under argon shield, the methanol solution that 60mL contains 0.82g (3.2mmol) AgOTf slowly is added drop-wise in the chloroform soln that 60mL contains 2.00g (1.5mmol) two endo compounds, stirring reaction 2h under room temperature.The whizzer separation gets settled solution after removing AgCl, and rotary evaporation desolventizes.Under argon shield, residue and 1.27g (4.5mmol) KBpz
4Be dissolved in the 50mL acetonitrile 61.5 ℃ of back flow reaction 24h.
After question response stops, being chilled to room temperature, filtering, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and gets crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization gets pure products 0.49g, and productive rate is 18.0%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.79(d，1H)，8.73(d，1H)，7.97(d，2H)，7.84(d，2H)，7.74(d，2H)，7.61(d，1H)，7.59(d，1H)，7.52(s，1H)，7.47(s，1H)，7.42(d，2H)，7.16(s，1H)，7.12(s，1H)，6.57(m，2H)，6.52(m，2H)，2.90(m，4H)，1.43(m，6H).
Embodiment 3
The present embodiment contain the iridium organic electroluminescence look phosphor material that turns blue, namely title complex two (2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium, wherein R is propyl group:
Title complex two (2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) to close the preparation technology of iridium as follows:
(1) 2,6-, two fluoro-3-boric acid pyridines synthetic identical with step (1) in case study on implementation 1;
(2) 2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl synthetic
Under nitrogen protection, (0.50mL, 4.00mmol) 2-bromo-4-propyl group pyridine, (0.76g, 4.80mmol) 2,6-two fluoro-3-boric acid pyridines, (0.28g, 0.24mmol) Pd (PPh
3)
4After being dissolved in 25mL toluene, adding the 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to 100 ℃ of reflux states, stirring reaction 18h.
After question response stops, after naturally being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=as elutriant carry out silica gel column chromatography separate at 1: 4, get colorless solid product 0.57g, yield is 60.8%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.57(d，1H)，8.48(d，1H)，7.73(s，1H)，7.66(d，1H)，6.97(d，1H)，2.97(m，2H)，1.89(m，2H)，0.98(m，3H).
Synthesizing of (3) two endo compounds
Under nitrogen protection, 1.87g (8mmol) 2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.
After question response stops, after naturally being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.87g, yield is 62.6%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.68(d，4H)，7.57(s，4H)，6.76(s，4H)，3.44(m，8H)，1.78(m，8H)，0.99(m，12H).
(4) title complex two (2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close the synthetic of iridium
Under nitrogen protection, the methanol solution that 60mL contains 0.82g (3.2mmol) AgOTf slowly is added drop-wise in the cellosolvo solution that 60mL contains 2.08g (1.5mmol) two endo compounds, stirring reaction 2h under room temperature.The whizzer separation gets settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 1.59g (5mmol) KBpz
4Be dissolved in the 60mL acetonitrile 135 ℃ of back flow reaction 24h.
After question response stops, being chilled to room temperature, filtering, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and gets crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization gets pure products 0.48g, and productive rate is 17.1%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.78(d，1H)，8.74(d，1H)，7.98(d，2H)，7.85(d，2H)，7.75(d，2H)，7.62(d，1H)，7.58(d，1H)，7.53(s，1H)，7.48(s，1H)，7.43(d，2H)，7.17(s，1H)，7.13(s，1H)，6.56(m，2H)，6.51(m，2H)，2.77(m，4H)，1.77(m，4H)，0.98(m，6H).
Embodiment 4:
The present embodiment contain the iridium organic electroluminescence look phosphor material that turns blue, namely title complex two (2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium, wherein R is butyl:
Title complex two (2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) to close the preparation technology of iridium as follows:
(1) 2,6-, two fluoro-3-boric acid pyridines synthetic identical with step (1) in case study on implementation 1;
(2) 2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl synthetic
Under nitrogen protection, (0.47mL, 4.00mmol) 2-bromo-4-butyl-pyridinium, (0.76g, 4.80mmol) 2,6-two fluoro-3-boric acid pyridines, (0.28g, 0.24mmol) Pd (PPh
3)
4After being dissolved in 25mL dimethyl sulfoxide (DMSO) (DMSO), adding the 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to 100 ℃ of reflux states, stirring reaction 18h.
After question response stops, after naturally being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=as elutriant carry out silica gel column chromatography separate at 1: 4, get colorless solid product 0.61g, yield is 61.4%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.59(d，1H)，8.50(d，1H)，7.74(s，1H)，7.68(d，1H)，6.99(d，1H)，2.92(m，2H)，1.81(m，2H)，1.13(m，2H)，0.89(m，3H).
Synthesizing of (3) two endo compounds
Under nitrogen protection, 1.99g (8mmol) 2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.
After question response stops, after naturally being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.85g, yield is 58.8%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.77(d，4H)，7.67(d，4H)，7.55(s，4H)，6.76(s，4H)，3.41(m，8H)，1.76(m，8H)，1.33(m，8H)，0.98(m，12H).
(4) Complex synthesis
Under nitrogen protection, the methanol solution that 60mL contains 0.82g (3.2mmol) AgOTf slowly is added drop-wise in the tetrahydrofuran solution that 60mL contains 2.17g (1.5mmol) two endo compounds, stirring reaction 2h under room temperature.The whizzer separation gets settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 1.91g (6mmol) KBpz
4Be dissolved in the 50mL acetonitrile 63.5 ℃ of back flow reaction 24h.
After question response stops, being chilled to room temperature, filtering, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and gets crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization gets pure products 0.44g, and productive rate is 15.2%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.79(d，1H)，8.75(d，1H)，7.97(d，2H)，7.85(d，2H)，7.76(d，2H)，7.62(d，1H)，7.58(d，1H)，7.53(s，1H)，7.48(s，1H)，7.43(d，2H)，7.17(s，1H)，7.14(s，1H)，6.56(m，2H)，6.51(m，2H)，2.67(m，4H)，1.75(m，4H)，1.31(m，4H)，0.98(m，6H).
Following embodiment 5 contains the iridium organic electroluminescence embodiment that the look phosphor material uses that turns blue in the luminescent layer of organic electroluminescence device.
Embodiment 5
The title complex two that the present embodiment makes with embodiment 1 (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (four pyrazoles boron) close iridium [(dfpyMepy)
2Ir6] as the organic electroluminescence device that the doping guest materials of luminescent layer makes, as shown in Figure 2, the structure of this organic electroluminescence device is the lamination assembling structure, is followed successively by: glass 11/ITO layer 12/PEDOT:PSS layer 13/PVK:(dfpyMepy)
2 Ir6 layer 14/BCP layer 15/Alq
3Layer 16/LiF layer 17/Al layer 18; Wherein, PVK is Polyvinyl carbazole; BCP is 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene; PEDOT is 3,4-Ethylenedioxy Thiophene; PSS is polystyrene-sulfonic acid matrix material.
This organic electroluminescence device, under the operating voltage of 9V, the blue light of device emission 465nm, device brightness is 3000cd/m
2
The manufacture craft of this organic electroluminescence device is as follows:
1, deposition one deck square resistance is tin indium oxide (ITO) layer of 10～20 Ω/mouths on a glass substrate, and as transparent anode, thickness is 200nm;
2, by spin coating technique, preparation one deck plays modification PEDOT:PSS layer on ITO, and as hole transmission layer, thickness is 30nm;
3, then at PEDOT:PSS layer surface spin coating one deck luminescent layer, thickness is 30nm, and the material of main part of this luminescent layer is PVK, and dopant material is (dfpyMepy)
2Ir6, i.e. PVK:(dfpyMepy)
2The Ir6 layer; (dfpyMepy)
2The doping ratio of Ir6 is 7wt%;
4, on luminescent layer successively vacuum evaporation one deck as the BCP layer (thickness is 10nm) of hole blocking layer, as the Alq3 layer (thickness is 30nm) of electronic injection transport layer with as the LiF (thickness is 1nm) of electronic injection buffer layer;
5, adopt at last vacuum coating technology, metal refining Al layer on buffer layer, thickness is 120nm, as the negative electrode of this organic electroluminescence device.
This organic electroluminescence device is owing to containing the higher iridium organic electroluminescent polymer of purity of color and fluorescence quantum efficiency in luminescent layer, it has higher effciency of energy transfer and luminous efficiency, can be widely used in the luminous fields such as blueness or white.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains the iridium organic electroluminescence look phosphor material that turns blue, and it is characterized in that, this contains the iridium organic electroluminescence look phosphor material that turns blue and has following general structural formula:
In formula, R is C
1～C
4Alkyl.
2. one kind contains the turn blue preparation method of look phosphor material of iridium organic electroluminescence, it is characterized in that, described preparation method comprises the steps:
In S1, oxygen-free environment, with general structure be
Compd A and three hydration iridous chlorides added in 3: 1～5: 1 in the first organic solvent according to mol ratio, after dissolving, be warming up to the first organic solvent reflux state, reaction generating structure general formula is
Two endo compound B; Wherein, R is C
1～C
4Alkyl;
In S2, oxygen-free environment, with described two endo compound B and structural formula be
Four pyrazoles boronation potassium added in 1: 2.5～1: 3.5 in the second organic solvent according to mol ratio, then add the first catalyzer in the second organic solvent, stir and to be warming up to the second organic solvent reflux state, the generating structure formula is
The described iridium organic electroluminescence look phosphor material that turns blue that contains.
3. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 2, is characterized in that, in step S1, described compd A is to adopt following step to make:
S11, in the anhydrous and oxygen-free environment, with structural formula be
Compound D and diisopropylamine lithium add at 1.2: 1 in tetrahydrofuran solution according to mol ratio, react under-78 ℃; Then add trimethyl borate toward reaction mixture, continue reaction at normal temperatures, the generating structure formula is
Compd E;
S12, with described compd E and general structure be
Compound F 17-hydroxy-corticosterone added the 3rd organic solvent that contains the second catalyzer in 1.5: 1～2: 1 according to mol ratio, be warming up under the 3rd organic solvent reflux state and carry out the Suzuki linked reaction, generate described compd A; Wherein, in described compound F 17-hydroxy-corticosterone, R is C
1～C
4Alkyl.
4. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 3, is characterized in that, also comprises the purification step to described compd E in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; Then be that the pH value of HCl aqueous solution conditioned reaction mixed solution of 3N is to neutral with equivalent concentration; Then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying.
5. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 3, is characterized in that, described step S12 also comprises the purification step to described compd A:
After adding distilled water in the reaction mixture that contains described compd A; Then extraction merges organic phase; Secondly use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Use at last ethyl acetate and normal hexane mixed solution to make eluent and the filtrate residue is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
6. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 3, is characterized in that, in step S12, described catalyzer is K
2CO
3The aqueous solution and Pd (PPh
3)
4Mixture; Described K
2CO
3Molar weight be 10 times of molar weight of described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4Molar weight be described compound F 17-hydroxy-corticosterone molar weight 0.5%.
7. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 3, is characterized in that, in step S12, described the 3rd organic solvent is tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO).
8. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 2, is characterized in that, in step S1, described the first organic solvent is cellosolvo.
9. the turn blue preparation method of look phosphor material of iridium organic electroluminescence that contains according to claim 2, is characterized in that, in step S2, described the second organic solvent is 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF); Described the first catalyzer is sodium methylate and silver trifluoromethanesulfonate.
10. an organic electroluminescence device, is characterized in that, the luminescent layer of this organic electroluminescence device comprises and contain the iridium organic electroluminescence look phosphor material that turns blue, and this contains the iridium organic electroluminescence look phosphor material that turns blue and has following general structure:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104305804A CN103172680A (en) | 2011-12-20 | 2011-12-20 | Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104305804A CN103172680A (en) | 2011-12-20 | 2011-12-20 | Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103172680A true CN103172680A (en) | 2013-06-26 |
Family
ID=48632931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104305804A Pending CN103172680A (en) | 2011-12-20 | 2011-12-20 | Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103172680A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178110A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic electroluminescent material, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664054A (en) * | 2004-02-02 | 2005-09-07 | 三星Sdi株式会社 | IR compound and organic electroluminescent device using the same |
| US20080038586A1 (en) * | 2004-07-16 | 2008-02-14 | Masato Nishizeki | White Light Emitting Organic Electroluminescence Element, Display and Illuminator |
| CN101172986A (en) * | 2002-08-16 | 2008-05-07 | 南加利福尼亚大学 | Organic light emitting materials with anionic ligand |
| US20090001875A1 (en) * | 2007-06-29 | 2009-01-01 | Yun Chi | Organic light-emitting device incorporating multifunctional osmium complexes |
| CN102146099A (en) * | 2010-02-09 | 2011-08-10 | 北京阿格蕾雅科技发展有限公司 | Synthesis method of organic-metallic iridium compound |
-
2011
- 2011-12-20 CN CN2011104305804A patent/CN103172680A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172986A (en) * | 2002-08-16 | 2008-05-07 | 南加利福尼亚大学 | Organic light emitting materials with anionic ligand |
| CN1664054A (en) * | 2004-02-02 | 2005-09-07 | 三星Sdi株式会社 | IR compound and organic electroluminescent device using the same |
| US20080038586A1 (en) * | 2004-07-16 | 2008-02-14 | Masato Nishizeki | White Light Emitting Organic Electroluminescence Element, Display and Illuminator |
| US20090001875A1 (en) * | 2007-06-29 | 2009-01-01 | Yun Chi | Organic light-emitting device incorporating multifunctional osmium complexes |
| CN102146099A (en) * | 2010-02-09 | 2011-08-10 | 北京阿格蕾雅科技发展有限公司 | Synthesis method of organic-metallic iridium compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178110A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic electroluminescent material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102899025B (en) | Containing iridium electroluminescent organic material and preparation method thereof and organic electroluminescence device | |
| CN102899024A (en) | Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device | |
| CN102898475A (en) | Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device | |
| CN102807856B (en) | Organic electroluminescent material containing iridium and preparation method thereof, and organic electroluminescence device | |
| CN102807857A (en) | Iridium-containing organic electroluminescent material and preparation method thereof and organic electroluminescent device | |
| CN103172679A (en) | Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device | |
| CN102899023B (en) | Containing iridium electroluminescent organic material and preparation method thereof and organic electroluminescence device | |
| CN103571454A (en) | Iridium containing organic electroluminescent material, preparation method thereof and organic electroluminescent device | |
| CN103173209B (en) | Containing iridium organic electroluminescence blue-light emitting material, its preparation method and organic electroluminescence device | |
| CN103172680A (en) | Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device | |
| CN102899022A (en) | Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device | |
| CN103172676A (en) | Iridium-containing organic electroluminescence material, preparation method and organic electroluminescent device | |
| CN102899026B (en) | Containing iridium electroluminescent organic material and preparation method thereof and organic electroluminescence device | |
| CN102807855B (en) | Iridium-containing organic electroluminescent material and preparation method thereof and organic electroluminescent device | |
| WO2013000166A1 (en) | Organic electroluminescent compound containing iridium, preparation method thereof and organic electroluminescent device | |
| CN104119396A (en) | Blue organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device | |
| CN104177409A (en) | Organic electroluminescence material and preparation method and application | |
| CN103666449A (en) | Blue-light organic electrophosphorescence material, and preparation method and application thereof | |
| CN103172675A (en) | Iridium-containing organic electroluminescence material, preparation method and organic electroluminescent device | |
| CN104877664A (en) | Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device | |
| CN103173210A (en) | Iridium-containing organic electroluminescence material, preparation method and organic electroluminescent device | |
| CN104177425A (en) | Blue light organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device | |
| CN103965875A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN102807524A (en) | Iridium-contained organic electroluminescent material, preparation method thereof and organic electroluminescent device | |
| CN102899021A (en) | Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130626 |