CN110642893A - Iridium metal complex and preparation method and device thereof - Google Patents
Iridium metal complex and preparation method and device thereof Download PDFInfo
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- CN110642893A CN110642893A CN201910924436.2A CN201910924436A CN110642893A CN 110642893 A CN110642893 A CN 110642893A CN 201910924436 A CN201910924436 A CN 201910924436A CN 110642893 A CN110642893 A CN 110642893A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 49
- -1 Iridium metal complex Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 125000001424 substituent group Chemical group 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 108091008695 photoreceptors Proteins 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an iridium metal complex, a preparation method and a device thereof, and relates to the field of organic photoelectric materials. The invention provides an iridium metal complex, which has a structure shown in a chemical formula 1:
Description
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an iridium metal complex and a preparation method and a device thereof.
Background
The organic electroluminescence technology is a latest generation flat panel display technology, which can be used for flat panel displays and illumination light sources, and currently, commercial flat panel displays have been put into the market. Illumination sources are also rapidly becoming industrialized due to their own absolute advantages. Electroluminescent devices have an all-solid-state structure, and organic electroluminescent materials are the core and foundation of the device. The development of new materials is a source for promoting the continuous progress of the electroluminescent technology. The preparation of the original material and the optimization of the device are also the research hotspots of the organic electroluminescent industry at present.
The phenomenon of phosphorescence has been pursued since the discovery, and since the luminous efficiency of phosphorescence materials is obviously higher than that of fluorescence, theoretically 100% luminous efficiency can be achieved, many research and development efforts of phosphor materials are being increased, and the industrialization development is attempted to be accelerated by phosphorescence materials. However, the phosphor material has high synthesis cost, high synthesis process requirement, high purification requirement, short service life and low efficiency, and is easy to pollute the environment in the synthesis process.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The novel iridium metal complex provided by the invention has the advantages that the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life is long.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides an iridium metal complex, which has a structure shown in a chemical formula 1:
in the formula, R1、R2、R3、R4And R5Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused ring group;
R1、R2、R3、R4、R5the substitution position is any position of the ring; r1、R2、R5The number of substituents is 0 to 4, R3The number of the substituents is 0 to 5, R4The number of the substituents is 0 to 3.
In the above technical scheme, R1、R2、R3、R4And R5Each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, or substituted or unsubstituted C8-C16 condensed ring group.
In the above technical scheme, the alkyl group is a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, a straight-chain alkyl group substituted by at least 1 substituent, a branched-chain alkyl group substituted by at least 1 substituent, or a cyclic alkyl group substituted by at least 1 substituent; wherein, the substituent is one or more of halogen, deuterium, cyano, hydroxyl and sulfydryl independently;
the aryl group is preferably an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxy or mercapto;
the aromatic heterocyclic group is preferably an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or mercapto.
In the above technical scheme, R1、R2、R3、R4、R5Can independently form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C60 aromatic ring, a substituted or unsubstituted C2-C60 aromatic heterocycle, a substituted or unsubstituted C6-C60 condensed ring or a substituted or unsubstituted C5-C60 spiro ring with other substituents on the ring;
or R1、R2、R3、R4Can mutually form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C60 aromatic ring, a substituted or unsubstituted C2-C60 aromatic heterocycle, a substituted or unsubstituted C6-C60 condensed ring or a substituted or unsubstituted C5-C60 spiro ring;
the substituent on the aliphatic ring, the aromatic heterocyclic ring, the condensed ring and the spiro ring is at least one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C8-C16 condensed ring group and substituted or unsubstituted C5-C60 spiro ring.
In the above technical solution, the iridium metal complex is optimally selected from any one of the following structures:
some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of the groups and the substituted groups and substituted positions thereof, which is not described in detail herein.
The invention also provides a preparation method of the iridium metal complex, which comprises the following steps:
mixing raw material A with iridium trichloride, and IrC13·3H2O, adding the mixture into ethylene glycol ethyl ether/water for full reaction to prepare a bridging ligand intermediate B; adding intermediate B and silver trifluoromethanesulfonate to CH2Cl2Fully reacting in MEOH to prepare an intermediate C; fully reacting the intermediate C with the intermediate D and anhydrous ETOH to obtain an iridium metal complex shown in a chemical formula 1;
the synthetic route is as follows:
in the formula, R1、R2、R3、R4And R5The groups are defined in chemical formula 1 and are not described herein.
The invention also provides an organic electroluminescent device prepared from the iridium metal complex shown in the chemical formula 1.
The organic electroluminescent device comprises: the iridium complex comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer contains the iridium metal complex shown in the chemical formula 1; the iridium metal complex may be present in the organic layer in a single form or in a mixture with other substances.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a hole injection and hole transport technical layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport and electron injection technical layer.
The organic electroluminescent device comprises at least one functional layer containing the iridium metal complex compound shown in the chemical formula 1.
The organic electroluminescent device comprises a light-emitting layer, wherein the light-emitting layer contains the iridium metal complex shown in the chemical formula 1. The light emitting layer includes a host material and a dopant material, and the dopant material contains an iridium metal complex represented by chemical formula 1 of the present invention. The mixing ratio of the main material of the luminescent layer to the doping material is 90: 10-99.5: 0.5.
The organic electroluminescent device can be used for an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
The invention has the beneficial effects that:
the novel iridium metal complex provided by the invention has the advantages that the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life is long.
The preparation method of the iridium metal complex provided by the invention is simple in process and suitable for industrial production.
Detailed Description
To further illustrate the process of the present invention, the following examples are set forth in more detail.
EXAMPLE 1 preparation of Compound L001
Weighing A-001 (64.5 mmol, 10g) and IrC1 of 2-phenylpyridine under the protection of nitrogen3·3H2O (24.8mmo1, 8.75g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. This gave bridging ligand B-001(6.64g, 50% yield) as a yellow powder.
② weighing intermediate B-001(4.67mmol, 5g), adding silver trifluoromethanesulfonate (14mmol, 3.6g), adding 100mL of dichloromethane, adding 40mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. Iridium complex intermediate C-001 was obtained as a yellow powder (6.2g, 93% yield).
③ weighing the intermediate C-001(8.4mmol, 6g), adding the ligand D-001(25.2mmol, 8.7g), adding 120mL of absolute ethyl alcohol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol and drying. The filtrate was concentrated and precipitated as a solid by silica gel column chromatography using methylene chloride as a solvent to obtain a final yellow compound, L0011.8g, in a yield of 25%).
HPLC purity is more than 99%.
Mass spectrum calculated 865.11; the test value was 865.10.
Elemental analysis calculated C: 68.03%; 4.89 percent of H; 4.86 percent of N; 22.22 percent of Ir.
The test value is 68.05 percent of C; 4.87 percent of H; 4.85 percent of N; 22.20 percent of Ir.
EXAMPLE 2 preparation of Compound L036
Weighing raw material A-036(59.10mmol, 10g) IrC1 under the protection of nitrogen3·3H2O(19.7mmo1, 7g) is put into a reaction system, 300mL of mixed solution of ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain yellow powder bridging ligand B-036(5.4g, the yield is 50%).
② secondly, weighing intermediate B-036(4.6mmol, 5g), adding silver trifluoromethanesulfonate (10.1mmol, 2.6 g), adding 100mL of dichloromethane, 30mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain intermediate C-036(5.36g, yield 80%) as yellow-green powder.
Thirdly, weighing intermediate C-036(6.9mmol, 5g), adding ligand D-036(20.7mmol, 9g), adding 100mL of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, performing suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, performing silica gel column chromatography, and performing filtration and concentration until solid is separated out to obtain final bright yellow compound L036(2g, yield 30%).
HPLC: the purity is more than 99%.
Mass spectrum calculated 962.29; the test value was 962.28.
Elemental analysis calculated C: 69.90%; 5.76 percent of H; 4.37 percent of N; 19.97 percent of Ir.
The test value is C: 69.92%; 5.75 percent of H; 4.38 percent of N; 19.98 percent of Ir.
EXAMPLE 3 preparation of Compound L074
Weighing raw material A-074(58.40mmol, 10g) IrC1 under the protection of nitrogen3·3H2O (19.5mmo1, 6.90g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, reflux is carried out for 18 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. This gave the bridging ligand B-074 as a yellow powder (5.0g, 45% yield).
② secondly, weighing intermediate B-074(4.4mmol, 5g), adding silver trifluoromethanesulfonate (11mmol, 2.5 g), adding 100mL of dichloromethane, 35mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain intermediate C-074(6g, 91% yield) as yellow-green powder.
Thirdly, weighing the intermediate C-074(8mmol, 6g), adding the ligand D-074(24mmol, 8.8g), adding 120mL of absolute ethyl alcohol into the system, refluxing for 12 hours under the protection of nitrogen, filtering, washing with alcohol and drying. The solid was concentrated by filtration using methylene chloride as a solvent and silica gel column chromatography to give the final bright yellow compound L074(1.5g, 21% yield).
HPLC: the purity is more than 99%.
Mass spectrum calculated 881.14; the test value was 881.20.
Elemental analysis calculated C: 68.16%; 5.26 percent of H; 4.77 percent of N; 21.81 percent of Ir.
The test value is 68.18 percent of C; 5.30 percent of H; 4.76 percent of N; 21.88 percent of Ir.
EXAMPLE 4 preparation of Compound L105
Weighing raw material A-105(43mmol, 10g) IrC1 under the protection of nitrogen3·3H2O (14.4mmo1, 5.1g) is put into a reaction system, 300mL of mixed solution of ethylene glycol ethyl ether and 100mL of purified water is added, reflux is carried out for 18 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain yellow powder bridging ligand B-105(4.4g, the yield is 50%).
② next weighing intermediate B-105(3.27mmol, 4g), adding silver trifluoromethanesulfonate (9.81mmol, 2.5 g), adding 80mL of dichloromethane, 25mL of methanol into the system, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, concentrating the filtrate of column chromatography (short column) until solid is separated out, obtaining intermediate C-105(4g, 77% yield) as yellow-green powder.
③ then weighing intermediate C-105(5.1mmol, 4g), adding ligand D-105(15.3mmol.7.3g), adding 120mL of absolute ethyl alcohol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, drying, using dichloromethane as solvent, carrying out silica gel column chromatography, filtering and concentrating until solid is separated out, obtaining the final bright yellow compound L105(1.73g, 30% yield).
HPLC: the purity is more than 99%.
Mass spectrum calculated 1128.51; the test value was 1128.50.
Elemental analysis calculated C: 73.44%; 5.81 percent of H; 3.72 percent of N; 17.03 percent of Ir.
The test value is C: 73.45%; 5.80 percent of H; 3.70 percent of N; 17.05 percent of Ir.
EXAMPLE 5 preparation of Compound L175
Weighing A-175(52.84mmol, 10g) and IrC1 under the protection of nitrogen3·3H2O (21.12mmo1, 7.45g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. Bridged ligand B-175 was obtained as a yellow powder (6.8g, 53% yield).
② weighing intermediate B-175(4.96mmol, 6g), adding silver trifluoromethanesulfonate (14.8mmol, 3.8g), adding 120mL of dichloromethane into the system, adding 40mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. Iridium complex intermediate C-175 was obtained as a yellow-green powder (7g, 90% yield).
③ weighing the intermediate C-175(7.67mmol, 6g), adding the ligand D-175(23.01mmol, 8.7g), adding 120mL of absolute ethyl alcohol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride and toluene as solvents, and the solid was precipitated by concentration to obtain the final bright yellow compound L175(1.8g, yield 23.5%).
HPLC purity greater than 99%.
Mass spectrum calculated 1000.39; the test value was 1000.38.
Elemental analysis calculated C68.44%; 6.75 percent of H; 5.60 percent of N; 19.21 percent of Ir.
The test value is C: 68.40%; 6.76 percent of H; 5.58 percent of N; 19.20 percent of Ir.
EXAMPLE 6 preparation of Compound L206
Weighing A-206(54.57mmol, 10g) IrC1 under the protection of nitrogen3·3H2O (18.2mmo1, 6.40g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. This gave bridging ligand B-206(5.3g, 51.5% yield) as a yellow powder.
② weighing intermediate B-206(4.44mmol, 5g), adding silver trifluoromethanesulfonate (13.3mmol, 3.4g), adding 100mL of dichloromethane into the system, adding 35mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. Iridium complex intermediate C-206 was obtained as a yellow powder (5.3g, 80% yield).
③ weighing the intermediate C-206(6.7mmol, 5g), adding the ligand D-206(20.1mmol, 5.8g), adding 150mL of absolute ethyl alcohol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride as a solvent to concentrate a solid to precipitate, thereby obtaining a final yellow compound L206(1.6g, yield 28.3%).
HPLC purity greater than 99%.
Mass spectrum calculated 870.13; the test value was 870.10.
Elemental analysis, calculated value C is 66.26 percent; 5.21 percent of H; 6.44 percent of N; 22.09 percent of Ir.
The test value is C: 66.25%; 5.22 percent of H; 6.42 percent of N; 22.10 percent of Ir.
The synthesis methods of other compounds are the same as those described above, and are not repeated herein, and the mass spectrum and the molecular formula of other synthesis examples are shown in the following table 1:
TABLE 1
| Compound (I) | Molecular formula | Calculated mass spectrum | Mass spectrometric test values |
| L015 | C43H31 D3IrN3 | 788.00 | 788.1 |
| L021 | C46H36 D4IrN3 | 831.09 | 831.1 |
| L049 | C51H42 IrN3 | 889.14 | 889.2 |
| L062 | C47H42 IrN3 | 841.09 | 841.1 |
| L085 | C45H32 D6IrN3 | 819.07 | 819.0 |
| L096 | C48H38 D6IrN3 | 861.15 | 861.2 |
| L142 | C60H46 IrN3 | 1001.27 | 1001.3 |
| L161 | C50H48 IrN3 | 883.19 | 883.2 |
| L183 | C46H26 D15IrN4 | 857.17 | 857.2 |
| L197 | C54H48 IrN3 | 931.22 | 931.2 |
The invention also provides an organic electroluminescent device which is made of the iridium metal complex of the formula 1.
In order to further describe the present invention, the following more specific examples are set forth
Example 7
An organic electroluminescent device is prepared using an iridium metal complex of formula L001, which is more specifically:
coating with a thickness of
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. Firstly, evaporating N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine ('2-TNATA') 60nm on an ITO (anode), and then evaporating NPB 60nm, a main substance 4,4'-N, N' -biphenyl dicarbazole ('CBP') and a doping substance compound F00190: 10 in a mixed ratio by weight, evaporating 30nm, evaporating 10nm of a hole blocking layer ('BALq') and 10nm of an electron transport layer ('Alq 3'), evaporating 0.2nm of an electron injection layer and evaporating 150nm of cathode Al to prepare the organic electroluminescent device. And testing the performance luminescence characteristics of the obtained device, wherein a KEITHLEY 2400 type source measuring unit and a CS-2000 spectral radiance luminance meter are adopted for measurement so as to evaluate the driving voltage, the luminescence brightness and the luminescence efficiency.
Corresponding organic electroluminescent devices were prepared by replacing the dopant compound F001 in example 7 with L036, L074, L105, L175, L206, L015, L021, L049, L062, L085, L096, L142, L161, L183, or L197, respectively.
Comparative example 1
An organic electroluminescent device was prepared in the same manner as in example 7, and the structure of the green light-doped compound of the light-emitting layer was as follows:
the same examination as in example 7 was performed on the prepared organic electroluminescent device, and the results are shown in table 2.
Table 2 test results of organic electroluminescent devices in example 7 and comparative example 1
As can be seen from Table 2, the organic electroluminescent device prepared using the compound provided by the present invention as a dopant material for the light emitting layer and the comparative compound Ir (ppy)3Compared with the organic electroluminescent device prepared by the doped material of the luminescent layer, the driving voltage is obviously reduced, and the luminous efficiency and the service life are obviously improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. An iridium metal complex, characterized by having a structure represented by chemical formula 1:
in the formula, R1、R2、R3、R4And R5Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or non-substitutedSubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed ring group;
R1、R2、R3、R4、R5the substitution position is any position of the ring; r1、R2、R5The number of substituents is 0 to 4, R3The number of the substituents is 0 to 5, R4The number of the substituents is 0 to 3.
2. The iridium metal complex of claim 1 wherein R is1、R2、R3、R4And R5Each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, or substituted or unsubstituted C8-C16 condensed ring group.
3. The iridium metal complex of claim 1 wherein the alkyl group is a straight chain alkyl group, a branched alkyl group, a cyclic alkyl group, a straight chain alkyl group substituted with at least 1 substituent group, a branched alkyl group substituted with at least 1 substituent group, or a cyclic alkyl group substituted with at least 1 substituent group; wherein, the substituent is one or more of halogen, deuterium, cyano, hydroxyl and sulfydryl independently;
the aryl group is an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxy or mercapto;
the aromatic heterocyclic group is an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or mercapto.
4. The iridium metal complex of claim 1 wherein R is1、R2、R3、R4、R5Each independently of the other substituted on the ringThe groups mutually form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C60 aromatic ring, a substituted or unsubstituted C2-C60 aromatic heterocycle, a substituted or unsubstituted C6-C60 condensed ring or a substituted or unsubstituted C5-C60 spiro ring;
or R1、R2、R3、R4Can mutually form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C60 aromatic ring, a substituted or unsubstituted C2-C60 aromatic heterocycle, a substituted or unsubstituted C6-C60 condensed ring or a substituted or unsubstituted C5-C60 spiro ring;
the substituent on the aliphatic ring, the aromatic heterocyclic ring, the condensed ring and the spiro ring is at least one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C8-C16 condensed ring group and substituted or unsubstituted C5-C60 spiro ring.
5. An iridium metal complex according to claim 1, which is selected from any one of the following structures:
6. a method for producing an iridium metal complex according to any one of claims 1 to 5, comprising the steps of:
mixing raw material A with iridium trichloride, and IrC13·3H2O, adding the mixture into ethylene glycol ethyl ether/water for full reaction to prepare a bridging ligand intermediate B; adding intermediate B and silver trifluoromethanesulfonate to CH2Cl2Fully reacting in MEOH to prepare an intermediate C; adding anhydrous ETOH into the intermediate C and the intermediate D, and fully reacting to obtain an iridium metal complex shown in a chemical formula 1;
the synthetic route is as follows:
in the formula, R1、R2、R3、R4And R5The groups are as defined in formula 1.
7. An organic electroluminescent device prepared from the iridium metal complex of any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 7, comprising: a first electrode, a second electrode, and an organic layer interposed between the two electrodes, wherein the organic layer contains the iridium metal complex of any one of claims 1 to 5; the iridium metal complex exists in the organic layer in a single form or in a mixture with other substances.
9. The organic electroluminescent device according to claim 8, comprising a light-emitting layer containing the iridium metal complex according to any one of claims 1 to 5.
10. The organic electroluminescent device according to claim 7, wherein the organic electroluminescent device is used for an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor.
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| CN111690016A (en) * | 2020-07-10 | 2020-09-22 | 奥来德(上海)光电材料科技有限公司 | Iridium coordination compound, preparation method thereof and photoelectric device |
| US20210047353A1 (en) * | 2019-08-14 | 2021-02-18 | Universal Display Corporation | Organic electroluminescent materials and devices |
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| US20210047353A1 (en) * | 2019-08-14 | 2021-02-18 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US20210280802A1 (en) * | 2020-02-20 | 2021-09-09 | Beijing Summer Sprout Technology Co., Ltd. | Organic electroluminescent material and device |
| CN111269269A (en) * | 2020-02-21 | 2020-06-12 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex, preparation method thereof and organic electroluminescent device |
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| CN111690016A (en) * | 2020-07-10 | 2020-09-22 | 奥来德(上海)光电材料科技有限公司 | Iridium coordination compound, preparation method thereof and photoelectric device |
| CN115403630A (en) * | 2021-05-27 | 2022-11-29 | 乐金显示有限公司 | Organometallic compound and organic electroluminescent device including the same |
| JP2022183130A (en) * | 2021-05-27 | 2022-12-08 | エルジー ディスプレイ カンパニー リミテッド | Organometallic compound and organic electroluminescent element comprising the same |
| WO2023085123A1 (en) * | 2021-11-15 | 2023-05-19 | キヤノン株式会社 | Organic compound and organic light-emitting element |
| WO2023120315A1 (en) * | 2021-12-22 | 2023-06-29 | キヤノン株式会社 | Organic compound and organic light-emitting element |
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