CN113121606A - Iridium complex with picolinic acid as auxiliary ligand and application thereof - Google Patents
Iridium complex with picolinic acid as auxiliary ligand and application thereof Download PDFInfo
- Publication number
- CN113121606A CN113121606A CN201911408902.8A CN201911408902A CN113121606A CN 113121606 A CN113121606 A CN 113121606A CN 201911408902 A CN201911408902 A CN 201911408902A CN 113121606 A CN113121606 A CN 113121606A
- Authority
- CN
- China
- Prior art keywords
- iridium complex
- groups
- ring
- alkyl
- group
- 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
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 67
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003446 ligand Substances 0.000 title claims abstract description 19
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title abstract description 22
- 229940081066 picolinic acid Drugs 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 9
- 229910052805 deuterium Inorganic materials 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- 150000008282 halocarbons Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 125000006822 tri(C1-C30) alkylsilyl group Chemical group 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 abstract description 9
- 230000008022 sublimation Effects 0.000 abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 150000002503 iridium Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- -1 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene HAT-CN Chemical compound 0.000 description 2
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- YWKKLBATUCJUHI-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C)=CC=1)C1=CC=CC=C1 YWKKLBATUCJUHI-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GBGPVUAOTCNZPT-UHFFFAOYSA-N 2-Methylcumarone Chemical compound C1=CC=C2OC(C)=CC2=C1 GBGPVUAOTCNZPT-UHFFFAOYSA-N 0.000 description 1
- GSKMWMFOQQBVMI-UHFFFAOYSA-N 2-bromo-5-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=C(Br)N=C1 GSKMWMFOQQBVMI-UHFFFAOYSA-N 0.000 description 1
- BPRWTROIQXSSOC-UHFFFAOYSA-N 4-(trifluoromethyl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=CC=N1 BPRWTROIQXSSOC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LFQSCWFLJHTTHZ-WFVSFCRTSA-N deuteriooxyethane Chemical compound [2H]OCC LFQSCWFLJHTTHZ-WFVSFCRTSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000000538 tail Anatomy 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 1
- ZQJYTTPJYLKTTI-UHFFFAOYSA-M zinc;2h-pyridin-2-ide;bromide Chemical compound Br[Zn+].C1=CC=N[C-]=C1 ZQJYTTPJYLKTTI-UHFFFAOYSA-M 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of electroluminescent materials, and relates to a novel iridium complex, wherein a main ligand of the iridium complex contains dibenzo heterocycle or aza-dibenzo heterocycle, and an auxiliary ligand of the iridium complex is picolinic acid or derivatives thereof. The dibenzoheterocycle or aza-dibenzoheterocycle in the iridium complex molecule is beneficial to regulating and controlling the luminescent color of the material and increasing the stability of the material. The iridium complex has high preparation yield, high purity, easy sublimation and purification and higher luminous efficiency, and devices prepared by the iridium complex serving as a luminescent material have excellent performance.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent devices (OLED), in particular to an iridium complex with a dibenzo heterocycle or aza-dibenzo heterocycle contained as a main ligand and picolinic acid or a derivative thereof as an auxiliary ligand and application of the iridium complex as a luminescent material in an organic electroluminescent device.
Background
An Organic Light-emitting Diode (OLED) is a phenomenon that an Organic Light-emitting material emits Light when excited by a current under the action of an electric field, and can convert electric energy into Light energy. Since the nodo, cauda dunqing, of kodak corporation, 1987 published the OLED of a low-voltage start-up high-efficiency high-brightness small-molecule organic thin film double-layer structure, the organic electroluminescent diode (OLED) has been extensively studied in the scientific and industrial fields.
The organic light emitting materials of early OLEDs were mainly conventional fluorescent materials emitting singlet excitons, which were only able to emit light using 25% of the singlet excitons at most, the remaining 75% of the triplet excitons were lost through nonradiative transition, while the phosphorescent materials emitted light using triplet excitons, while the singlet states were transferred to the triplet states through intersystem crossing (ISC), and thus the phosphorescent devices could achieve 100% quantum efficiency. In recent years, a great deal of research has shown that, among many phosphorescent materials, iridium complexes are considered to be the most desirable choice for OLEDs phosphorescent materials. The iridium complex is more suitable for the application in the field of photoelectric function due to higher luminous efficiency and good photo-thermal stability, and the luminous color of the iridium complex can be more easily adjusted by regulating and controlling the ligand. Therefore, the iridium complex becomes a research hotspot in the field of electroluminescent materials.
As is known, the iridium complex luminescent material has good electronic transmission performance, can balance the transmission of carriers, broaden the carrier composite region and improve the efficiency of devices, and has important research significance for improving the performance of the devices. And the high-efficiency material and the working stability of the device are of great importance, and the material with high efficiency and high stability has fewer reports. In addition, the synthesis yield and sublimation purification yield of the complex for practical materials are critical to reduce the manufacturing cost of materials and devices. Therefore, it is necessary to provide an iridium complex luminescent material with excellent device performance, good thermal stability, stable chemical properties and high preparation yield.
Disclosure of Invention
Aiming at the defects of the prior art, the invention designs a novel iridium complex with a main ligand containing dibenzo heterocycle or aza-dibenzo heterocycle and an auxiliary ligand being picolinic acid or derivatives thereof, and applies the material to an organic electroluminescent device to provide a novel high-efficiency luminescent material for an OLED device.
The specific technical scheme of the invention is as follows:
an iridium complex is characterized in that a main ligand of the iridium complex contains a dibenzo-heterocycle or aza-dibenzo-heterocycle, and an auxiliary ligand is picolinic acid or a derivative thereof. The structural general formula of the iridium complex is as follows:
wherein Ring A and Ring B are bonded by a C-C bond and Ir and Ring B are bonded by an Ir-C bond.
R1-R3Independently represent the case where the corresponding ring may be mono-, di-, tri-, tetra-or unsubstituted.
Wherein R is1Represents 1 to 4 substituents on the pyridine ring, R2Represents 1 to 4 on the A ringSubstituent, R3Represents 1 to 4 substituents on the C ring, R1-R3Identical or different, when each represents a plurality of substituents on the corresponding ring, these substituents, identical or different, being chosen from hydrogen, deuterium, halogen groups, amino groups, nitrile groups, or the following groups, unsubstituted or substituted by deuterium or halogen groups: alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, silyl, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, carboxylic acid, ester, or alkylthio.
Wherein X is O, S or Se.
Wherein A is1、A2、A3、A4Identical or different, represents carbon or nitrogen, and A1、A2、A3、A4At least one of which is carbon.
Wherein B is1、B2、B3、B4Identical or different, represents carbon or nitrogen, and B1、B2、B3、B4At least one of which is carbon.
Preferably, the main ligand structure of the iridium complex of the invention is as follows:
The preferable structure of the iridium complex is as follows:
Preferably, R1-R3Selected from hydrogen, deuterium, halogen groups, amino groups, nitrile groups, or the following unsubstituted or substituted with deuterium or halogen groups: C1-C6 alkyl, C3-C10 cycloalkyl, C1-C10 heteroalkyl, wherein the heteroatom is selected from O or S, C1-C6 alkoxy, phenoxy, tri (C1-C30) alkylsilyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C6 aldehyde, C1-C6 carboxylic acid group, C1-C6 ester group or C1-C6 alkylthio, any position is substituted by hydrogen, C1-C6 alkyl, halogen groupA phenyl, pyridyl, pyrimidinyl, furyl or thienyl group substituted by a group or by a halogenated hydrocarbon group of C1-C6.
Further preferably, R is1Selected from hydrogen, C1-C6 alkyl, halogen group, C1-C6 halogenated hydrocarbon group, phenyl substituted by hydrogen at any position, C1-C6 alkyl, halogen group or C1-C6 halogenated hydrocarbon group, pyridyl, pyrimidyl, furyl or thienyl.
Preferably, R in the structural formula of the iridium complex2，R3Selected from the group consisting of hydrogen, halogen, halogenated hydrocarbon groups, alkyl groups, deuterium, deuterated alkyl groups, heteroalkyl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, aryl groups, and heteroaryl groups.
More preferably, R in the structural general formula of the iridium complex2Is the following group:
more preferably, R in the structural general formula of the iridium complex3The alkyl chain representing C1-C4 is the following group:
preferably, the iridium complex has the following structure:
the iridium complexes of the invention may be prepared by conventional methods, for example by reacting a primary ligand with IrCl3In moleRefluxing for 10-24 hours in ethylene glycol ethyl ether according to the ratio of 2:1, cooling and filtering to obtain an iridium chlorine bridge complex; then refluxing the iridium chlorine bridge complex and picolinic acid in ethylene glycol ethyl ether for 10-24 hours in the presence of sodium carbonate to obtain a crude product of the iridium complex, performing column chromatography to obtain a pure product, and further performing sublimation purification under a vacuum condition to obtain the luminescent material meeting the requirements of the preparation device.
The invention also aims to provide application of the iridium complex as a luminescent material in preparation of organic electroluminescent devices, photocatalysts and optical probes.
The iridium complex can be used for preparing an organic electroluminescent device, for example, the organic electroluminescent device comprises a substrate, an anode, a hole injection material, a hole transport layer, an organic luminescent layer, an electron transport layer, an electron injection material and a cathode. The substrate is glass, the anode is indium tin oxide, the hole injection layer is 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene HAT-CN, the hole layer is made of 4,4' -cyclohexyl bis [ N, N-bis (4-methylphenyl) aniline TAPC material, the electron transport layer is made of 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] benzene TmPyPb, the electron injection material is LiF, and the cathode is metal Al; the organic light-emitting layer comprises a main material and a light-emitting material, wherein the main material is 4,4' -tri (9-carbazolyl) triphenylamine TCTA, and the light-emitting material is the iridium complex.
The invention has the beneficial effects that: the iridium complex has the advantages of good thermal stability, stable chemical property, simple preparation, high yield and easy sublimation and purification, and compared with the traditional luminescent material, the prepared device has more excellent performance, and can provide greater application value for the design and production of organic electroluminescent displays and lighting sources.
Detailed Description
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that this example is intended to illustrate the invention and not to limit the scope of the invention in any way.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
EXAMPLE 1 preparation of Iridium Complex AG002 of the present invention
Preparation of Main ligand L1-1: 2-bromopyridine (11.8mmol), dibenzofuran-7-methyl-4-boronic acid (14.2mmol), and tetrakis (triphenylphosphine) palladium (0.12mmol) as a catalyst were dissolved in 45mL of a mixture of tetrahydrofuran: water (volume ratio 2:1) with potassium carbonate (30.0mmol), and the mixture was stirred under reflux for 24 hours under a nitrogen atmosphere. After the reaction is finished, cooling to room temperature, separating liquid, extracting the water phase with ethyl acetate, collecting the organic phase, drying with anhydrous magnesium sulfate, and separating the product by using a 200-300-mesh silica gel column chromatography to obtain 9.44mmol of main ligand L1-1 with the yield of 80%.
Preparation of the chloro-bridged compound C1: iridium trichloride (IrCl)3.nH2O, Ir mass% w ═ 54.5%, 2.9mmol) and L1-1(6.0mmol) were dissolved in 40mL of a mixture of ethylene glycol ethyl ether and water (volume ratio: 3:1), and the mixture was refluxed at 130 ℃ for 20 hours. After cooling, a yellow precipitate precipitated out, which was filtered off and washed to give 1.3mmol of product in 90% yield.
Preparing an iridium complex AG 002: the chloro-bridged compound C1(0.90mmol), picolinic acid (2.26mmol), and sodium carbonate (2.26mmol) were added to the flask, ethylene glycol ethyl ether as a solvent, and refluxed under nitrogen for 20 h. After the reaction is finished, separating the product by silica gel column chromatography, further recrystallizing by using dichloromethane and petroleum ether to obtain 1.34mmol of product with the yield of 76%, further carrying out sublimation purification by using a sublimation device, analyzing the obtained iridium complex AG002 by using high-resolution mass spectrometry, and testing the purity by using HPLC (high performance liquid chromatography).
Example 2 preparation of Iridium Complex AG038 of the present invention
The preparation of AG038 was carried out according to the experimental protocol of example 1, except that the primary ligand was prepared using 2-bromo-5- (trifluoromethyl) pyridine instead of the 2-bromopyridine of example 1, to give AG 038.
Example 3 preparation of an Iridium Complex AG070 according to the invention
The preparation of AG070 was carried out according to the experimental protocol of example 1, except that 4- (trifluoromethyl) pyridine-2-carboxylic acid was used instead of picolinic acid in example 1, to give AG 070.
Example 4 preparation of Iridium Complex AG014 of the invention
Preparation of Main ligand L4-2: adding 2-methylbenzofuran [2,3-b ] into a flask]pyridin-8-yl-Trifluoromethanesulfonate (24.1mmol), Pd2(dba)3(0.48mmol) and X-Phos (1.93mmol) are added dropwise with 2 times of equivalent of 2-pyridyl zinc bromide (0.5M, tetrahydrofuran solution) under nitrogen atmosphere, the reaction is stirred under reflux for 5 hours, after the reaction is finished, the product is separated by 200-300 mesh silica gel column chromatography, and the white solid product 5.6g is obtained with the yield of 80%.
Preparation of the chloro-bridged Compound C4-2: iridium trichloride (IrCl)3.nH2O, Ir mass% w ═ 54.5%, 2.9mmol) and L4-2(6.0mmol) were dissolved in 40mL of a mixture of ethylene glycol ethyl ether and water (volume ratio: 3:1), and the mixture was refluxed at 130 ℃ for 20 hours. After cooling, a yellow precipitate precipitated out, which was filtered off and washed to give 1.23mmol of product in 85% yield.
Preparation of iridium complex AG 014: the chloro-bridged compound C4-2(0.90mmol), picolinic acid (2.26mmol), and sodium carbonate (2.26mmol) were added to the flask, ethylene glycol ethyl ether as a solvent, and refluxed under nitrogen for 20 h. After the reaction is finished, separating the product by silica gel column chromatography, further recrystallizing by using dichloromethane and petroleum ether to obtain 1.32mmol of product with yield of 75%, further sublimating and purifying by using a sublimating device, analyzing the obtained iridium complex AG014 by using high resolution mass spectrometry, and testing the purity by using HPLC.
Example 5 preparation of Iridium Complex AG019 of the present invention
Preparation of Main ligand L5-3: under a nitrogen atmosphere, L4-2(6.15mmol), sodium ethoxide (12.3mmol), ethanol-d 1(25ml) were added to the flask, and stirred at reflux for 60 h. And (3) after the reaction is finished, removing the solvent by spinning, adding a proper amount of water and ethyl acetate, layering, drying the organic phase, and separating the product by using a 200-300-mesh silica gel column chromatography to obtain a white solid product 5.22mmol with the yield of 85%.
Preparation of the chloro-bridged Compound C5-3: iridium trichloride (IrCl)3.nH2O, Ir mass content w% (-) 54.5%, 2.9mmol) and L5-3(6.0mmol) were dissolved in 40mL of a mixed solution of ethylene glycol ethyl ether and water (volume ratio: 3:1), and the mixture was stirred and refluxed for 20 hours. Cooling, precipitating to give yellow precipitate, and filteringWashing to obtain 1.2mmol of product with 83% yield.
Preparing an iridium complex AG 019: the chloro-bridged compound C5-3(0.90mmol), picolinic acid (2.26mmol), and sodium carbonate (2.26mmol) were added to the flask, ethylene glycol ethyl ether as a solvent, and refluxed under nitrogen for 20 h. After the reaction is finished, separating the product by silica gel column chromatography, further recrystallizing by using dichloromethane and petroleum ether to obtain 1.46mmol of product with the yield of 81%, further carrying out sublimation purification by using a sublimation device, analyzing the obtained iridium complex AG019 by using a high-resolution mass spectrometry, and testing the purity by using HPLC.
The high resolution mass spectrum, sublimation yield, and HPLC data of the iridium complexes prepared in examples 1 to 5 are shown in table 1.
TABLE 1
Example 6 preparation of Iridium Complex AG002 organic electroluminescent device
The structure of the OLEDs device includes: a substrate, an anode, a hole injection material, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection material, and a cathode. The substrate is glass, the anode is indium tin oxide, the hole injection layer is 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene HAT-CN (5nm), and the evaporation rate is 0.05 nm/s; the hole layer adopts 4,4' -cyclohexyl di [ N, N-di (4-methylphenyl) aniline TAPC material (50nm), and the evaporation rate is 0.05 nm/s; the electron transport layer adopts 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene TmPyPb (50nm), and the evaporation rate is 0.05 nm/s; the electron injection material is LiF (1nm), and the evaporation rate is 0.01 nm/s; the cathode is metal Al (100nm), and the evaporation rate is 0.2 nm/s; the organic light-emitting layer is of a doped structure, the thickness of the organic light-emitting layer is 40nm, the organic light-emitting layer comprises a main material and a light-emitting material, the main material is 4,4' -tris (9-carbazolyl) triphenylamine TCTA, the light-emitting material is an iridium complex AG002, and the mass fraction of the iridium complex is 6 wt%. The light emitting characteristics of the prepared devices were measured using an I-V-L test system (model: M761, brand: McScience), and the device properties are shown in Table 2.
Example 7 preparation of Iridium Complex AG014 organic electroluminescent device
The difference from example 6 is that the light-emitting material used was an iridium complex AG014, and device properties are shown in table 2.
Example 8 preparation of Iridium Complex AG019 organic electroluminescent device
The difference from example 6 is that the luminescent material used was iridium complex AG019, and device properties are shown in table 2.
Example 9 preparation of Iridium Complex AG038 organic electroluminescent device
The difference from example 6 is that the luminescent material used is iridium complex AG038, and the device properties are shown in table 2.
Example 10 preparation of Iridium Complex AG070 organic electroluminescent device
The difference from example 6 is that the light-emitting material used was iridium complex AG070, and the device properties are shown in table 2.
COMPARATIVE EXAMPLE Iridium Complex (ppy)2Preparation of Ir (pic) organic electroluminescent device
The difference from example 6 is that the luminescent material used is an iridium complex (ppy)2Ir (pic), device performance is shown in table 2.
The functional materials have the following structures:
TABLE 2
| Device with a metal layer | Luminescent material | Starting voltage | Power efficiency | Quantum efficiency | Color of light emission |
| Example 6 | AG02 | 0.97 | 1.65 | 1.55 | Green light |
| Example 7 | AG014 | 1.06 | 1.56 | 1.6 | Green light |
| Example 8 | AG019 | 0.98 | 1.39 | 1.4 | Green light |
| Example 9 | AG038 | 1.01 | 1.63 | 1.39 | Green light |
| Example 10 | AG070 | 0.96 | 1.35 | 1.52 | Green light |
| Comparative example | (ppy)2Ir(pic) | 1 | 1 | 1 | Green light |
Table 2 illustrates: starting voltage, power efficiency, quantum efficiency are based on a comparative example set to 1.
From the results in tables 1 and 2, it can be seen that the iridium complex of the present invention is easy to sublimate and purify, has high yield, and has better performance in device performance than the known OLED light-emitting material (comparative example). The luminescent device of the invention is not completely optimized, but only schematically proves the performance and industrial application prospect of the red light material used by the device.
The iridium complex provided by the invention can be used as a luminescent material to be applied to a luminescent layer of OLEDs. While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (9)
1. An iridium complex is characterized by the following structural general formula:
wherein Ring A and Ring B are bonded by a C-C bond, and Ir and Ring B are bonded by an Ir-C bond;
wherein R is1Represents 1 to 4 substituents on the pyridine ring, R2Represents 1 to 4 substituents on the ring A, R3Represents 1 to 4 substituents on the C ring, R1-R3Identical or different, when each represents a plurality of substituents on the corresponding ring, these substituents, identical or different, being chosen from hydrogen, deuterium, halogen groups, amino groups, nitrile groups, or the following groups, unsubstituted or substituted by deuterium or halogen groups: alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, silyl, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, carboxylic acid, ester, or alkylthio;
wherein X is O, S or Se;
wherein A is1、A2、A3、A4Identical or different, represents carbon or nitrogen, and A1、A2、A3、A4At least one of which is carbon.
Wherein B is1、B2、B3、B4Identical or different, represents carbon or nitrogen, and B1、B2、B3、B4At least one of which is carbon.
2. An iridium complex according to claim 1, wherein the iridium complex has the following primary ligand structure:
B1represents carbon or nitrogen.
3. The iridium complex according to claim 2, characterized by the following structure:
4. The iridium complex according to claim 1, wherein R is1-R3Selected from hydrogen, deuterium, halogen groups, amino groups, nitrile groups, or the following unsubstituted or substituted with deuterium or halogen groups: C1-C6 alkyl, C3-C10 cycloalkyl, C1-C10 heteroalkyl, wherein the heteroatom is selected from O or S, C1-C6 alkoxy, phenoxy, tri (C1-C30) alkylsilyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C6 aldehyde, C1-C6 carboxylic acid group, C1-C6 ester group or C1-C6 alkylthio, phenyl, pyridyl, pyrimidyl, furyl or thienyl, wherein any position of the phenyl, pyridyl, pyrimidyl, furyl or thienyl is substituted by hydrogen, C1-C6 alkyl, halogen group or C1-C6 halogenated hydrocarbon group.
5. The iridium complex according to claim 1, wherein R is1Selected from hydrogen, C1-C6 alkyl, halogen group, C1-C6 halogenated hydrocarbon group, phenyl substituted by hydrogen at any position, C1-C6 alkyl, halogen group or C1-C6 halogenated hydrocarbon group, pyridyl, pyrimidyl, furyl or thienyl.
6. The iridium complex according to claim 1, wherein R is2Selected from the group consisting of:
7. the iridium complex according to claim 1, wherein R is3The alkyl chain representing C1-C4 is selected from the following groups:
8. the iridium complex according to claim 1, wherein the iridium complex is selected from the following structures:
9. use of an iridium complex as claimed in any one of claims 1 to 8 as a luminescent material in the preparation of organic electroluminescent devices, photocatalysts and optical probes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911408902.8A CN113121606A (en) | 2019-12-31 | 2019-12-31 | Iridium complex with picolinic acid as auxiliary ligand and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911408902.8A CN113121606A (en) | 2019-12-31 | 2019-12-31 | Iridium complex with picolinic acid as auxiliary ligand and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113121606A true CN113121606A (en) | 2021-07-16 |
Family
ID=76770040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911408902.8A Pending CN113121606A (en) | 2019-12-31 | 2019-12-31 | Iridium complex with picolinic acid as auxiliary ligand and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113121606A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920783A (en) * | 2022-06-29 | 2022-08-19 | 北京云基科技有限公司 | Luminescent material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802382A (en) * | 2003-06-09 | 2006-07-12 | 日立化成工业株式会社 | Metal coordination compound, polymer composition, and organic electroluminescence element using them |
| US20170069848A1 (en) * | 2015-09-09 | 2017-03-09 | Universal Display Corporation | Organic electroluminescent materials and devices |
-
2019
- 2019-12-31 CN CN201911408902.8A patent/CN113121606A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802382A (en) * | 2003-06-09 | 2006-07-12 | 日立化成工业株式会社 | Metal coordination compound, polymer composition, and organic electroluminescence element using them |
| US20170069848A1 (en) * | 2015-09-09 | 2017-03-09 | Universal Display Corporation | Organic electroluminescent materials and devices |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920783A (en) * | 2022-06-29 | 2022-08-19 | 北京云基科技有限公司 | Luminescent material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102584939B1 (en) | Metal complex with fluorine substitution | |
| JP2010537975A (en) | Organometallic complex derivative and organic light emitting device using the same | |
| JP7458483B2 (en) | Metal complexes and their uses | |
| CN111777633B (en) | Boron-containing compound and organic electroluminescent device containing same | |
| CN110305149B (en) | Thermal activation delayed fluorescent material and application thereof | |
| KR20130129543A (en) | New compound and organic light emitting device using the same | |
| CN110218212B (en) | Nitrogen heterocyclic compound, display panel and display device | |
| CN113121607B (en) | Red light iridium complex with main ligand containing quinoline/quinazoline and application | |
| CN113121608B (en) | Iridium complex with main ligand containing dibenzoheterocycle or aza-dibenzoheterocycle and application thereof | |
| JP7402979B2 (en) | Platinum metal complexes and their applications in organic electroluminescent devices | |
| CN113121606A (en) | Iridium complex with picolinic acid as auxiliary ligand and application thereof | |
| CN115073307B (en) | Fluorene compound and application thereof in organic electroluminescent device | |
| EP3444257B1 (en) | Organic electroluminescent material and organic electroluminescent device | |
| CN116063267A (en) | Spiro compound and application thereof | |
| CN116063229A (en) | Organic compound and application thereof in organic electroluminescent device | |
| CN114736148A (en) | Triarylamine compound, organic material containing triarylamine compound, and organic light-emitting device | |
| CN114702395A (en) | Triarylamine compound and organic electroluminescent device comprising the same | |
| KR101647172B1 (en) | New compound and organic light emitting device using the same | |
| CN114685287B (en) | Triarylamine compound and organic electroluminescent device comprising same | |
| CN114621193B (en) | Organic light-emitting material, method for manufacturing the same, and OLED device | |
| KR102201026B1 (en) | Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode | |
| CN110698505B (en) | Compound, display panel and display device | |
| CN116425805A (en) | Tetradentate platinum complex luminescent material containing spiro structure and application thereof | |
| CN116396335A (en) | Tetradentate platinum complex luminescent material based on tetraarylethylene skeleton structure and application thereof | |
| CN112266353A (en) | Aromatic anthracene organic light-emitting compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210716 |