CN113402563B - Iridium complex, preparation method thereof, organic electroluminescent device and display device - Google Patents
Iridium complex, preparation method thereof, organic electroluminescent device and display device Download PDFInfo
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 10
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 28
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 100
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 238000005406 washing Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 239000008213 purified water Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 5
- 150000002503 iridium Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical group C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- -1 amino, hydroxyl Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
-
- 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
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an iridium complex, a preparation method thereof, an organic electroluminescent device and a display device, belonging to the field of organic photoelectric materials, wherein the iridium complex has a structural general formula as follows:
Description
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an iridium complex, a preparation method thereof, an organic electroluminescent device and a display device.
Background
With the development of multimedia information technology, users have higher and higher requirements for the performance of display devices such as flat panels, notebooks, and the like. Compared with liquid crystal display devices, organic electroluminescent devices (OLEDs) do not need a backlight source, and have the advantages of wider viewing angle, low power consumption, high response speed and the like, so the OLEDs have wider application prospects.
Among them, the luminescent materials of OLEDs are mainly phosphorescent luminescent materials, and the metal iridium complex is a phosphorescent luminescent material which is widely studied at present. However, the conventional OLEDs using the iridium complex as a light emitting material still have the problems of high driving voltage, low light emitting efficiency, short service life, and the like.
Disclosure of Invention
An object of the embodiments of the present invention is to provide an iridium complex to solve the problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an iridium complex has a general structural formula of formula I:
wherein m is a positive integer of not more than 3, and when m is 3, an a ring is absent; when m is 1 or 2, the ring A is a cyclic structure;
a. b and c are integers, a is more than or equal to 0 and less than or equal to 4, b is more than or equal to 0 and less than or equal to 2, and c is more than or equal to 1 and less than or equal to 4;
x is O or S, Y is N or P;
R 1 、R 2 and R 3 Is at any position of the ring and is independently selected from at least one of hydrogen, deuterium, amino, hydroxyl, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C5-C30 spiro ring; and at least one R 3 Is fluorine.
Wherein two or more substituents R in the same molecule 1 、R 2 And R 3 May have different meanings. R is 1 ，R 2 ，R 3 Or can form an aromatic ring or an aromatic heterocyclic ring or a ring system with the ring on which the compound is arranged.
Specifically, the a ring may be one of a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring. Preferably, R 1 ，R 2 ，R 3 At least one group of (a) and (b) thereofIs of annular ring structure.
Preferably, the structural general formula of the iridium complex is any one of formula 01 to formula 04:
in the formula, R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-to 30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group; r 7 And R 8 At any position of the ring; r 7 ，R 8 Or can form an aromatic ring or an aromatic heterocyclic ring or a ring system with the ring; d. e, f, g and h are integers, d is more than or equal to 0 and less than or equal to 1, e is more than or equal to 0 and less than or equal to 2, f is more than or equal to 0 and less than or equal to 2, g is more than or equal to 0 and less than or equal to 4, and h is more than or equal to 0 and less than or equal to 4. Preferably, R 7 And/or R 8 And the ring-shaped structure with the ring-shaped structure. Preferably, the iridium complex has a chemical structural formula of any one of the following formulas:
although specific structural forms are listed above, the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of some simple groups, substituted groups and substituted positions thereof, which are not described in detail herein.
Another object of the embodiments of the present invention is to provide a preparation method of the iridium complex, which includes the following steps:
reacting the raw material A with iridium trichloride to obtain an intermediate B;
reacting the intermediate B with the raw material C to obtain the iridium complex; or reacting the intermediate B with silver trifluoromethanesulfonate to obtain an intermediate C, and then reacting the intermediate C with the raw material D to obtain the iridium complex;
wherein the structural formulas of the raw material A and the raw material D are respectively and independently formula A-01 or formula A-02:
the structural formula of the raw material C is represented by formula C-01:
specifically, the synthetic route of formula 01 is as follows:
the synthetic route for formula 02 is as follows:
the synthetic route for formula 03 is as follows:
the synthetic route for formula 04 is as follows:
another object of the embodiments of the present invention is to provide an application of the iridium complex in preparation of organic electroluminescent devices.
Another object of an embodiment of the present invention is to provide an organic electroluminescent device, which includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer includes the iridium complex described above.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely comprises the iridium complex. Specifically, the iridium complex is in a single form or is mixed with other substances and exists in the organic layer. Preferably, the organic layer includes at least one or more of a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport technologies, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a layer having both electron transport and electron injection technologies. Preferably, the mixing ratio of the main material to the doping material is 90: 10-99.5: 0.5. Preferably, the organic electroluminescent device may be used for an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor.
Another object of an embodiment of the present invention is to provide a display apparatus, including a functional module and a display module, where the display module includes the above organic electroluminescent device.
Compared with the prior art, the embodiment of the invention has the beneficial effects that: according to the iridium complex provided by the embodiment of the invention, the specific heterocyclic ligand is selected to be coordinated and combined with iridium, so that the wavelength of the iridium complex can be adjusted, and after the iridium complex is used for an organic electroluminescent device, the luminous efficiency of the organic electroluminescent device can be obviously improved, the service life of the organic electroluminescent device can be prolonged, and the driving voltage of the organic electroluminescent device can be reduced. In addition, the preparation method of the iridium complex provided by the embodiment of the invention has the advantages of simple process and high purity of the prepared product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The iridium complexes described below are used as examples in the examples of the present invention, and the preparation methods of the other iridium complexes are similar and will not be further illustrated herein.
Example 1
This example provides an iridium complex of formula i-2, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
ligand A-2(14.57g,50mmol), IrC1 was weighed out under nitrogen protection 3 ·3H 2 O (7.76g,22mmo1) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 purified water is added, the mixture is refluxed for 25 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. The mass of the bridged ligand B-2 obtained was 9.42g in the form of a dark red powder, with a yield of 53%.
Then weighing the bridged ligand B-2(8.90g,5.5mmol), adding anhydrous potassium carbonate (7.59g,55mmol), adding 170ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-2(2.20g,22mmol) under nitrogen, refluxing for 24 hours under nitrogen protection, cooling, suction filtering, washing with alcohol and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, and concentrating the filtrate to precipitate solid, thereby finally obtaining the iridium complex shown in the formula I-2, wherein the mass of the iridium complex is 3.64 g. The yield was 38% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 871.96; the test value was 871.43.
The calculated value of the elemental analysis (%) is 59.23; h is 3.81; f is 4.36; 22.04 parts of Ir; n is 3.21; o is 7.34, and the test value C is 59.25; h is 3.82; f is 4.38; 22.02 parts of Ir; n is 3.20; o is 7.32.
Example 2
This example provides an iridium complex of formula I-11, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing ligand A-11 under nitrogen protection system21.07g,50mmol),IrC1 3 ·3H 2 O (7.76g,22mmo1) is put into a reaction system, a mixed solution of 420m1 ethylene glycol ethyl ether and 140m1 purified water is added, the mixture is refluxed for 25 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. The mass of the bridged ligand B-11 obtained was 11.99g in the form of a dark red powder, in 51% yield.
Then weighing the bridging ligand B-11(11.75g,5.5mmol), adding anhydrous potassium carbonate (7.59g,55mmol), adding 230ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-11(3.27g,16.5mmol) under nitrogen, refluxing for 24 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the iridium complex shown in the formula I-11, wherein the mass of the iridium complex is 4.33 g. The yield was 32% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1230.39 test 1230.16.
The calculated value of the elemental analysis (%) is 66.38; h is 4.34; f is 6.18; 15.62 parts of Ir; 2.28 of N; o is 5.20, and the test value is 66.35; h is 4.32; f is 6.17; 15.65 parts of Ir; 2.28 of N; o is 5.23.
Example 3
This example provides an iridium complex of formula I-44, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
ligand A-44(25.28g,60mmol), IrC1 was weighed out under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 500m1 ethylene glycol ethyl ether and 167m1 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. The mass of the bridged ligand B-44 was 12.61g, a dark red powder was obtained in 59% yield.
Then weighing the bridging ligand B-44(10.68g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 210ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-44(3.18g,15mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as solvent, using neutral alumina column chromatography, concentrating the filtrate, and precipitating solid to obtain iridium complex shown in formula I-44 with mass of 4.23 g. The yield was 34% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1244.32; the test value was 1244.19.
The calculated value of the elemental analysis (%) is C: 60.81; h is 4.13; f is 12.21; 15.45 parts of Ir; 2.25 of N; o is 5.14, and the test value is C is 60.80; h is 4.10; f is 12.22; 15.43 parts of Ir; 2.28 of N; o is 5.16.
Example 4
This example provides an iridium complex of formula I-62, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
ligand A-62(14.79g,44mmol), IrC1 was weighed out under nitrogen protection 3 ·3H 2 Adding O (7.05g,20mmo1) into a reaction system, adding a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 pure water, refluxing for 28 hours under the protection of nitrogen, cooling to room temperature, precipitating, filtering the precipitate, washing with water, absolute ethyl alcohol and petroleum ether in sequence, and drying. The mass of the bridged ligand B-62 was 11.68g, which was obtained as a dark red powder in 65% yield.
Then weighing the bridging ligand B-62(10.78g,6mmol), adding anhydrous potassium carbonate (8.28g,60mmol), adding 210ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-62(7.21g,30mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, and concentrating the filtrate to precipitate solid, thereby finally obtaining the iridium complex shown in the formula I-62 with the mass of 5.55 g. The yield was 42% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1102.06; the test value was 1102.40.
Elemental analysis (%): calculated value is C: 53.40; h is 3.57; f, 17.24; 17.44 parts of Ir; n is 2.54; o is 5.81, and the test value is 53.41; h is 3.59; f, 17.25; 17.44 parts of Ir; n is 2.51; o is 5.80.
Example 5
This example provides an iridium complex of formula I-83, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing the formula A-83(20.06g,54mmol), IrC1 under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 410m1 ethylene glycol ethyl ether and 140m1 purified water is added, the mixture is refluxed for 28 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. The mass of the bridged ligand B-83 obtained was 11.23g in the form of a dark red powder, in 58% yield.
Then weighing the bridging ligand B-83(9.68g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 200ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-83(4.61g,20mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Dichloromethane is used as a solvent, neutral alumina column chromatography is carried out, filtrate is concentrated, solid is precipitated, and finally the iridium complex shown in the formula I-83 is obtained, wherein the mass of the iridium complex is 3.37 g. The yield was 29% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1162.29; the test value was 1162.53.
Elemental analysis (%): calculated value is C: 63.04; h is 4.34; f is 8.17; 16.54 parts of Ir; 2.41 of N; o is 5.51, and the test value is C is 63.06; h is 4.35; f is 8.18; 16.52 parts of Ir; 2.40 of N; o is 5.50.
Example 6
This example provides an iridium complex of formula i-96, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing the formula A-96(21.26g,50mmol), IrC1 under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) is put into a reaction system, mixed solution of 420m1 ethylene glycol ethyl ether and 140m1 purified water is added, the mixture is refluxed for 28 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. The mass of the bridged ligand B-96 was 10.98g, which was obtained in the form of a dark red powder, in 51% yield.
Then weighing the bridging ligand B-96(10.76g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 210ml of ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-96(7.05g,25mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, and concentrating and separating out solid from filtrate to finally obtain the iridium complex shown in the formula I-96, wherein the mass of the iridium complex is 3.17 g. The yield was 24% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1321.72; the test value was 1321.41.
Elemental analysis (%): calculated value is C: 39.08; h is 0.61; f, 38.81; 14.54 parts of Ir; 2.12 of N; o:4.84, test value C: 39.09; h is 0.63; 38.84 is used as a reference material; 14.52 parts of Ir; 2.11 of N; o is 4.81.
Example 7
This example provides an iridium complex of formula i-100, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing formula A-100(9.31g,60mmol), IrC1 under nitrogen protection 3 ·3H 2 Adding O (20mmo1,7.05g) into a reaction system, adding a mixed solution of 180m1 ethylene glycol ethyl ether and 60m1 purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand B-100 was obtained as a yellow powder (4.61g, 43% yield).
Weighing the intermediate B-100(4.29g and 4mmol), adding silver trifluoromethanesulfonate (2.26g and 8.8mmol), adding 90ml of dichloromethane into the system, adding 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. The iridium complex intermediate of formula C-100 was obtained as a yellow powder (5.52g, 97% yield).
Weighing the intermediate C-100(4.98g,7mmol), adding the ligand D-100(6.43g,17.5mmol), adding 100ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The filtrate was concentrated by column chromatography on silica gel using methylene chloride as solvent to give the final yellow compound of formula I-100 (1.27g, 21% yield) with an HPLC purity of greater than 99%.
Mass spectrum calculated 867.02 test 867.30.
Elemental analysis (%). calcd for C: 65.11; h is 3.84; f is 2.19; 22.17 parts of Ir; n is 4.85; o is 1.85, and the test value is 65.12; h is 3.86; f is 2.19; 22.15 parts of Ir; n is 4.85; o is 1.86.
Example 8
This example provides an iridium complex of formula I-114, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
formula A-114(14.57g,50mmol), IrC1 was weighed out under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) was put into the reaction system, and 290m1 ethylene glycol was addedRefluxing a mixed solution of diethyl ether and 97m1 purified water for 28 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate by suction, and washing and drying the precipitate by water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand form B-114 was obtained as a yellow powder (5.66g, 35% yield).
Weighing the intermediate B-114(5.66g,3.5mmol), adding silver trifluoromethanesulfonate (2.76g,10.5mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-114(6.27g, 91% yield) was obtained as a yellow powder.
Weighing the intermediate C-114(5.90g,6mmol), adding the ligand A-114(5.24g,18mmol), adding 120ml of absolute ethyl alcohol into the system, refluxing for 36 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-114 (1.66g, 26% yield) was obtained by silica gel column chromatography using dichloromethane and toluene as solvents and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.
Mass spectrum calculated 1063.17; the test value was 1063.28.
The calculated value of the elemental analysis (%) > is C: 64.39; h is 3.70; f is 5.36; 18.08 parts of Ir; n is 3.95; o is 4.51, and the test value is C is 64.38; h is 3.71; f is 5.34; 18.07 parts of Ir; n is 3.97; o is 4.52.
Example 9
This example provides an iridium complex of formula I-138, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing A-138(14.57g,50mmol), IrC1 of formula A-138 under nitrogen protection system 3 ·3H 2 Adding O (7.05g,20mmo1) into reaction system, adding mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 purified water, refluxing for 30 hours under nitrogen protection, cooling to room temperature, precipitating, filtering, washing with water, anhydrous ethanol and petroleum ether, oven drying. The bridged ligand form B-138(8.24g, 51% yield) was obtained as a yellow powder.
Weighing the intermediate B-138(8.08g,5mmol), adding silver trifluoromethanesulfonate (5.25g,20mmol), adding 160ml of dichloromethane into the system, adding 53ml of methanol, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-138(8.76g, 89% yield) was obtained as a yellow powder.
Weighing the intermediate C-138(8.36g,8.5mmol), adding the ligand D-138(9.91g,34mmol), adding 170ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-138 (2.64g, 31% yield) was obtained by silica gel column chromatography using toluene as solvent and concentrating the filtrate to precipitate a solid with an HPLC purity of greater than 99%.
Mass spectrum calculated 1003.14; the test value was 1003.57.
The calculated value of the elemental analysis (%) > is C: 65.85; h is 3.82; f is 3.79; 19.16 parts of Ir; n is 4.19; o is 3.19, and the test value is C is 65.87; h is 3.85; f is 3.79; 19.17 parts of Ir; n is 4.16; o is 3.16.
Example 10
This example provides an iridium complex of formula i-157, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
weighing A-157(10.32g,50mmol), IrC1 of formula A under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 210m1 ethylene glycol ethyl ether and 70m1 purified water is added, the mixture is refluxed for 30 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-157(6.51g, 51% yield) was obtained as a yellow powder.
Weighing the intermediate B-157(5.74g,4.5mmol), adding silver trifluoromethanesulfonate (3.54g,13.5mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 36 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-157(6.89g, 94% yield) was obtained as a yellow powder.
Weighing the intermediate C-157(6.51g,8mmol), adding the ligand D-157(6.19g,20mmol), adding 130ml of absolute ethanol into the system, refluxing for 30 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-157 (1.82g, 25% yield) was obtained by silica gel column chromatography using dichloromethane as solvent and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.
Mass spectrum calculated 911.18; the test value was 911.43.
The calculated value of the elemental analysis (%) > is C: 61.95; h is 6.41; f is 4.17; 21.10 parts of Ir; n is 4.61; o is 1.76, and the test value is C is 61.95; h is 6.41; f is 4.17; 21.10 parts of Ir; n is 4.61; o is 1.76.
Example 11
This example provides an iridium complex of formula I-176, which is prepared by the following reaction scheme:
the specific preparation method comprises the following steps:
formula A-176(17.95g,60mmol), IrC1 was weighed under nitrogen protection 3 ·3H 2 O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 330m1 ethylene glycol ethyl ether and 110m1 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. The bridged ligand B-176 was obtained as a yellow powder (6.43g, 39% yield).
Weighing the intermediate B-176(5.77g,3.5mmol), adding silver trifluoromethanesulfonate (1.98g,7.7mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-176(6.58g, 94% yield) was obtained as a dark yellow powder.
Weighing the intermediate C-176(6.00g,6mmol), adding the ligand D-176(7.65g,18mmol), adding 120ml of absolute ethanol into the system, refluxing for 28 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-176 (1.89g, 26% yield) was obtained by silica gel column chromatography using dichloromethane and toluene as solvents and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.
Mass spectrum calculated 1212.62; the test value was 1212.90.
The calculated value of the elemental analysis (%) is 38.63; f, 40.73; 15.85 of Ir; n is 3.47; o is 1.32, and the test value is C38.62; f, 40.71; 15.83 parts of Ir; n is 3.49; o is 1.35.
The synthesis methods of other iridium complexes are the same as those described above, and the mass spectrum or the molecular formula of other synthesis examples are shown in table 1 below:
TABLE 1
| Compound (I) | Molecular formula | Calculated mass spectrum | Calculated mass spectrum |
| Formula I-1 | C 39 H 21 D 4 F 2 IrN 2 O 4 | 819.88 | 819.50 |
| Formula I-24 | C 43 H 23 F 12 IrN 2 O 4 | 1051.86 | 1051.42 |
| Formula I-35 | C 61 H 51 F 4 IrN 2 O 4 | 1144.30 | 1144.07 |
| Formula I-55 | C 63 H 67 D 2 F 2 IrN 2 O 4 | 1150.48 | 1150.76 |
| Formula I-79 | C 39 H 6 D 2 F 19 IrN 2 O 4 | 1123.70 | 1123.24 |
| Formula I-107 | C 50 H 32 F 2 IrN 3 O | 921.04 | 921.62 |
| Formula I-121 | C 75 H 44 F 4 IrN 3 O 2 | 1287.41 | 1287.18 |
| Formula I-130 | C 57 H 33 F 9 IrN 3 O 3 | 1171.11 | 1171.64 |
| Formula I-146 | C 58 H 35 D 9 F 2 IrN 3 O 2 | 1054.28 | 1054.60 |
| Formula I-166 | C 49 H 31 F 13 IrN 3 O | 1117.00 | 1117.49 |
The embodiment of the invention also provides an organic electroluminescent device prepared by using the iridium complex provided by the embodiment, and specifically, the organic electroluminescent device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.
The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one layer may or may not include the iridium complex.
Specifically, the light-emitting layer includes a host material and a dopant material; wherein, the host material can be 4,4'-N, N' -biphenyl dicarbazole (CBP), but is not limited thereto; the doping material may be the iridium complex.
In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.
Device example 1
Embodiment 1 of the device provides a red phosphorescent organic electroluminescent device, and the preparation method comprises the following steps:
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. Under vacuum conditions, the standard pressure was set at 1X 10 -6 And (4) supporting. Thereafter, the ITO substrate was coated with CuPc
CBP + Iridium Complex represented by formula I-1 (5%)
And
the sequence of (a) and (b) forming layers of organic material.
Referring to the above-mentioned method, the iridium complexes represented by the formula I-1 were replaced with iridium complexes represented by the formulae I-2, I-11, I-24, I-35, I-44, I-55, I-62, I-79, I-83, and I-96, respectively, to prepare organic electroluminescent devices of the corresponding compounds.
Comparative device example 1
Method as provided in device example 1An organic electroluminescent device was produced, except that the doping material of the luminescent layer (iridium complex represented by formula I-1) was replaced with (btp) 2 Ir(acac)。
Among them, the compounds used in the embodiments of the present invention are copper (II) phthalocyanine (CuPc), NPB, (btp) 2 Ir(acac)，Alq 3 And the structural formula of CBP is as follows:
the organic electroluminescent device prepared as above was subjected to the driving voltage, current efficiency and service life (T95) tests, and the results are shown in table 2.
TABLE 2
| Doping material for device | Drive voltage (V) | Current (mA) | Current efficiency (cd/A) | T95(h) |
| (btp) 2 Ir(acac) | 8.1 | 9 | 16.9 | 560 |
| Formula I-1 | 3.4 | 9 | 35.7 | 1070 |
| Formula I-2 | 3.2 | 9 | 36.4 | 1050 |
| Formula I-11 | 3.7 | 9 | 39.1 | 1030 |
| Formula I-24 | 3.1 | 9 | 34.2 | 1040 |
| Formula I-35 | 3.3 | 9 | 37.2 | 990 |
| Formula I-44 | 3.4 | 9 | 36.1 | 1060 |
| Formula I-55 | 3.8 | 9 | 35.1 | 1040 |
| Formula I-62 | 3.0 | 9 | 35.7 | 1100 |
| Formula I-79 | 3.5 | 9 | 35.6 | 1060 |
| Formula I-83 | 3.2 | 9 | 39.5 | 1070 |
| Formula I-96 | 3.6 | 9 | 34.6 | 1040 |
As can be seen from table 1, compared with the existing doped material, under the same current condition, the iridium complex provided by the embodiment of the invention has a lower driving voltage, and the current efficiency and the service life are obviously higher.
Device example 2
Embodiment 2 of the device provides a green phosphorescent organic electroluminescent device, and the preparation method comprises the following steps:
coating with a thickness of
I of (A)The TO glass substrate was cleaned in distilled water 2 times, ultrasonically cleaned for 30 minutes, repeatedly cleaned with distilled water 2 times, ultrasonically cleaned for 10 minutes, and after the cleaning with distilled water was completed, the substrate was ultrasonically cleaned in the order of isopropanol, acetone, methanol, and the like, dried, transferred TO a plasma cleaning machine, cleaned 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-1, 4-diamine ('2-TNATA') 60nm on an ITO (anode), then evaporating NPB 60nm, a host substance 4,4'-N, N' -biphenyl dicarbazole ('CBP') and a doping material (an iridium complex shown in a formula I-100) according to a weight ratio of 90:10, mixing and evaporating 30nm, evaporating a hole blocking layer ('BALq') 10 nm), evaporating an electron transport layer ('Alq 3') 40 nm), evaporating an electron injection layer LiF 0.2nm and evaporating cathode Al 150nm to prepare the organic electroluminescent device. The performance luminescence characteristics of the obtained device are tested by adopting a KEITHLEY 2400 type source measuring unit and a CS-2000 spectral radiance luminance meter to evaluate the driving voltage, the service life and the luminescence efficiency.
Referring to the above-mentioned method, the iridium complexes represented by the formulae I-100 are replaced with iridium complexes represented by the formulae I-107, I-114, I-121, I-130, I-138, I-146, I-157, I-166, and I-176, respectively, to prepare organic electroluminescent devices of the corresponding compounds.
Comparative device example 2
An organic electroluminescent device was fabricated by the method provided in device example 2, except that the doping material (iridium complex represented by formula I-100) of the light-emitting layer was replaced with Ir (ppy) 3 . Wherein, Ir (ppy) 3 The structural formula of (A) is as follows:
the organic electroluminescent device prepared as above was examined for driving voltage, luminous efficiency and service life (T95), and the results are shown in table 3.
TABLE 3
| Doping material for device | Drive voltage (V) | Luminance (cd/cm) 2 ) | Efficiency (cd/A) | T95(h) |
| Ir(ppy) 3 | 6.0 | 5000 | 23.0 | 56.1 |
| Formula I-100 | 3.1 | 5000 | 83.4 | 780 |
| Formula I-107 | 3.3 | 5000 | 86.8 | 761 |
| Formula I-114 | 3.4 | 5000 | 87.5 | 792 |
| Formula I-121 | 3.8 | 5000 | 85.6 | 801 |
| Formula I-130 | 4.0 | 5000 | 88.1 | 826 |
| Formula I-138 | 3.5 | 5000 | 79.9 | 751 |
| Formula I-146 | 3.7 | 5000 | 84.2 | 781 |
| Formula I-157 | 3.9 | 5000 | 90.0 | 792 |
| Formula I-166 | 3.8 | 5000 | 86.5 | 738 |
| Formula I-176 | 3.2 | 5000 | 81.9 | 827 |
As can be seen from Table 2, the organic electroluminescent device prepared by using the iridium complex provided by the embodiment of the invention as the doping material of the light-emitting layer and the conventional iridium complex Ir (ppy) 3 Compared 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.
Another object of an embodiment of the present invention is to provide a display apparatus, including a functional module and a display module, where the display module includes the above organic electroluminescent device. Specifically, the display device may be a mobile phone, a notebook computer, a tablet computer, and the like, but is not limited thereto.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. An iridium complex is characterized in that the structural general formula of the iridium complex is any one of formula 01-formula 04:
in the formula, a, b and c are integers, a is more than or equal to 0 and less than or equal to 4, b is more than or equal to 0 and less than or equal to 2, and c is more than or equal to 1 and less than or equal to 4;
x is O or S, Y is N or P;
R 1 、R 2 and R 3 Is at any position of the ring and is independently selectedAt least one of hydrogen, deuterium, fluorine, C1-C30 alkyl, C3-C30 cycloalkyl, fluorine substituted or unsubstituted C6-C30 aryl, and C10-C30 condensed ring group; and at least one R 3 Is fluorine;
R 4 、R 5 、R 6 、R 7 and R 8 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-to 30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group; r 7 And R 8 At any position of the ring;
d. e, f, g and h are integers, d is more than or equal to 0 and less than or equal to 1, e is more than or equal to 0 and less than or equal to 2, f is more than or equal to 0 and less than or equal to 2, g is more than or equal to 0 and less than or equal to 4, and h is more than or equal to 0 and less than or equal to 4.
2. An iridium complex according to claim 1, wherein the iridium complex has a chemical structure of any one of the following formulae:
3. a method for producing an iridium complex according to any one of claims 1 to 2, comprising the steps of:
reacting the raw material A with iridium trichloride to obtain an intermediate B;
reacting the intermediate B with the raw material C to obtain the iridium complex; or reacting the intermediate B with silver trifluoromethanesulfonate to obtain an intermediate C, and then reacting the intermediate C with the raw material D to obtain the iridium complex;
wherein the structural formulas of the raw material A and the raw material D are respectively and independently formula A-01 or formula A-02:
the structural formula of the raw material C is represented by formula C-01:
4. use of an iridium complex as claimed in any one of claims 1 to 2 in the preparation of an organic electroluminescent device.
5. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the iridium complex as claimed in any one of claims 1 to 2.
6. An organic electroluminescent device according to claim 5, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely comprises the iridium complex.
7. A display device comprising a functional module and a display module, characterized in that the display module comprises the organic electroluminescent device as claimed in claim 5 or 6.
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| JP2012006878A (en) * | 2010-06-25 | 2012-01-12 | Mitsubishi Chemicals Corp | Organometallic complex, luminescent material, organic electroluminescent element material, organometallic complex-containing composition, organic electroluminescent element, organic el display, and organic el illumination |
| CN104177426A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Blue phosphorescence iridium metal complex, preparation method thereof, and organic electroluminescent device |
| KR101765199B1 (en) * | 2014-12-15 | 2017-08-07 | (주)위델소재 | Iridium complex compounds and organic electroluminescent device using the same |
| CN110698517B (en) * | 2019-09-27 | 2022-05-20 | 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 |
| CN110669077A (en) * | 2019-09-27 | 2020-01-10 | 吉林奥来德光电材料股份有限公司 | Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device |
| CN111471072A (en) * | 2019-11-21 | 2020-07-31 | 吉林奥来德光电材料股份有限公司 | Organic iridium metal complex and preparation method and application thereof |
| CN111057112A (en) * | 2019-12-24 | 2020-04-24 | 吉林奥来德光电材料股份有限公司 | Phosphorescent compound and preparation method and application thereof |
| CN111825724B (en) * | 2020-07-28 | 2023-04-28 | 奥来德(长春)光电材料科技有限公司 | Phosphorescent iridium complex, preparation method thereof and electroluminescent device |
| CN112010908B (en) * | 2020-08-31 | 2023-03-24 | 奥来德(上海)光电材料科技有限公司 | Iridium complex for red light electroluminescent material, preparation method thereof and photoelectric device |
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