CN110922432A - Iridium metal complex, preparation method thereof and organic electroluminescent device - Google Patents
Iridium metal complex, preparation method thereof and organic electroluminescent device Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 55
- -1 Iridium metal complex Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 2
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 claims description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 101100490051 Lactococcus lactis subsp. lactis (strain IL1403) accD gene Proteins 0.000 description 1
- 241000985284 Leuciscus idus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an iridium metal complex, a preparation method thereof and an organic electroluminescent device, wherein the structural formula of the iridium metal complex is shown as a chemical formula 1, the iridium metal complex with a novel structure provided by the invention is combined by selecting a specific heterocyclic ligand, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for the organic electroluminescent device, so that the luminous efficiency of the device is improved, and the starting voltage is reduced.
Description
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an iridium metal complex, a preparation method thereof and an organic electroluminescent device.
Background
Organic light emitting diodes are also called organic electroluminescent displays, organic light emitting semiconductors. It was found in the laboratory in 1979 by professor deng dunqing cloud of chinese ethnic. The OLED display technology has the advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, extremely high reaction speed and the like. However, the price of the high-end display screen is more expensive than that of the liquid crystal television. The organic electroluminescence technology is a latest generation flat panel display technology, and can be used for flat panel displays and illumination light sources, and currently, commercial flat panel displays are put into the market, and the illumination light sources are rapidly industrialized due to their own absolute advantages. The electroluminescent device has an all-solid-state structure, organic electroluminescent materials are the core and the foundation of the device, and the development of new materials is the source power for promoting the continuous progress of the electroluminescent technology. The preparation of the original material and the optimization of the device are also the research hotspots of the organic electroluminescent industry at present.
The phosphorescence luminescent phenomenon is always favored since the discovery, because the luminescent efficiency of the phosphorescence material is obviously higher than the luminescent efficiency of the fluorescence, theoretically reaching 100 percent of the luminescent efficiency, many scientific research institutions are increasing the research and development of the phosphorescence material and trying to accelerate the industrialized development through the phosphorescence material; however, the phosphor material has high synthesis cost, high synthesis process requirements, high purification requirements and low efficiency, and easily pollutes the environment in the synthesis process.
Disclosure of Invention
The iridium metal complex with a novel structure provided by the invention is combined by selecting a specific heterocyclic ligand, and the wavelength of the compound is adjusted, so that the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the starting voltage of the device is reduced.
In order to achieve the purpose, the invention provides the following technical scheme:
an iridium metal complex having a structural formula shown in chemical formula 1:
wherein: r1、R2、R3Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, or substituted or unsubstituted C8-C16 condensed ring group, R4Is substituted or unsubstituted alkane, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C4-C6 aromatic heterocyclic group.
As a further scheme of the invention: r4Is a substituted or unsubstituted alkyl group.
As a further scheme of the invention: r1、R2、R3The substitution position is any position of the ring; r1And R2The number of the substituents is 0-3, R3The number of substituents is 0-2.
As a still further scheme of the invention: the alkyl is straight-chain alkyl, branched-chain alkyl, cycloalkyl, straight-chain alkyl substituted by at least 1 substituent, branched-chain alkyl substituted by at least 1 substituent or cycloalkyl substituted by at least 1 substituent; wherein, the substituent is one or more of halogen, deuterium, cyano and hydroxyl independently.
As a still further scheme of the invention: the aryl group is preferably an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, deuterium, amino, cyano, nitro or hydroxy.
As a still further scheme of the invention: the aromatic heterocyclic group is preferably an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro or hydroxyl;
R1、R2、R3each independently forms a substituted or unsubstituted C3-C12 aliphatic ring, a substituted or unsubstituted C6-C12 aromatic ring, a substituted or unsubstituted C2-C12 aromatic heterocycle, a substituted or unsubstituted C6-C12 condensed ring with the ring;
or R1And R2、R2And R3Form a substituted or unsubstituted C3-C12 aliphatic ring, a substituted or unsubstituted C6-C12 aromatic ring, a substituted or unsubstituted C2-C12 aromatic heterocycle, a substituted or unsubstituted C6-C12 fused ring, or a substituted or unsubstituted C5-C12 spiro ring;
the substituent on the substituent group is at least one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C12 aryl and substituted or unsubstituted C4-C12 aromatic heterocyclic group.
In the above-described aspect, it is most preferable that the iridium metal complex is selected from any one of the following structures.
Some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of the groups and the substituted groups and substituted positions thereof, which is not described in detail herein.
The preparation method of the iridium metal complex comprises the following steps:
1) providing compound a and compound C, respectively, represented by the following structural formulae:
2) fully reacting the raw material A with iridium trichloride to prepare a bridging ligand intermediate B;
3) and fully reacting the intermediate B with the intermediate C to obtain the iridium metal complex shown in the chemical formula 1.
As a still further scheme of the invention: the structure of bridging ligand intermediate B is:
the synthetic route is as follows:
wherein: r1、R2、R3、R4And the number and chemical formula of the respective substituents1 are consistent.
An organic electroluminescent device comprises the iridium metal complex, a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer comprises the iridium metal complex shown in the chemical formula 1; the iridium metal complex of chemical formula 1 of the present invention may be present in the organic material layer in a single form or in a mixture with other materials.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
The organic electroluminescent device comprises at least one functional layer containing an iridium metal complex represented by chemical formula 1 of the present invention.
The organic electroluminescent device includes a light emitting layer containing an iridium metal complex represented by chemical formula 1 of the present invention. Preferably, the light emitting layer of the organic electroluminescent device includes a host material and a dopant material, and the dopant material is an iridium metal complex represented by chemical formula 1 of the present invention. Further preferably, the mixing ratio of the host material and the doping material of the light-emitting layer is 90:10-99.5: 0.5.
The device of the invention can be used for an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
Compared with the prior art, the invention has the beneficial effects that: the iridium metal complex with the novel structure provided by the invention has the advantages that the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency and the brightness of the device are improved.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An iridium metal complex L001, namely a compound with the number of L001, comprises the following specific synthetic steps:
1) weighing A-001(86.5mmol, 20g) and IrCl under nitrogen protection system3·3H2Adding O (28.9mmo 110.2 g) into a reaction system, adding a mixed solution of 600mL of ethylene glycol ethyl ether and 200mL of purified water, refluxing for 24 hours at 120 ℃ under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and sequentially washing and drying with water, absolute ethyl alcohol and petroleum ether to obtain a red-powder bridged ligand B-001(12g, the yield is 60%);
2) weighing the intermediate B-001(8.65mmol, 12g), adding a ligand acetylacetone C-001(25.95mmol, 2.6g), adding 250mL of ethylene glycol ethyl ether and potassium carbonate (12g) into the system, stirring at 120 ℃ for 24 hours under the protection of nitrogen, performing suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, performing silica gel column chromatography, and concentrating the filtrate to separate out a solid to obtain a final red compound L001(3.1g, the yield is 23.8%);
HPLC purity is more than 99.5 percent;
mass spectrum calculated 757.91; the test value was 757.90.
Elemental analysis, calculated value C is 58.64%; 4.39 percent of H; 7.39 percent of N; 4.22 percent of O; 25.36 percent of Ir; the test value is C: 58.60%; 4.40 percent of H; 7.40 percent of N; 4.25 percent of O; 25.40 percent of Ir;
specifically, the reaction formulae of steps 1) to 2) are as follows:
in the embodiment, the iridium metal complex is applied to preparation of organic electroluminescent device products.
Example 2
An iridium metal complex L032, namely a compound with the number of L032, is synthesized by the following steps:
1) weighing A-032(86.5mmol, 20g) and IrCl under the protection of nitrogen3·3H2Placing O (28.9mmo1, 10.2g) into a reaction system, adding a mixed solution of 600mL of ethylene glycol ethyl ether and 200mL of purified water, refluxing for 24 hours at 120 ℃ 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 to obtain a red powdered bridging ligand B-032(12.3g, the yield is 62%);
2) intermediate B-032(8.9mmol, 12.3g) was weighed, ligand C-032(26.7mmol, 4.2g) was added, 250mL of ethylene glycol ethyl ether and potassium carbonate (12.3g) were added to the system, and the mixture was stirred at 120 ℃ for 24 hours under nitrogen protection, filtered, washed with alcohol, dried, and subjected to silica gel column chromatography using methylene chloride as a solvent to obtain a solid, which was concentrated and precipitated as a final red compound L032(4.3g, yield 29.8%).
HPLC purity is more than 99.6%.
Mass spectrum calculated 807.93; the test value was 807.90.
Elemental analysis calculated C: 57.98%; h, 3.87 percent; 10.40 percent of N; 3.96 percent of O; 23.79 percent of Ir; the test value is that C is 58.00 percent; h, 3.89 percent; 10.45 percent of N; 3.98 percent of O; 23.80 percent of Ir.
Specifically, the reaction formulae of steps 1) to 2) are as follows:
in the embodiment, the iridium metal complex is applied to preparation of organic electroluminescent device products.
Example 3
An iridium metal complex L057, namely a compound with the number of L057, comprises the following specific synthetic steps:
1) a-057(80.5mmol, 20g) IrCl was weighed under a nitrogen protection system3·3H2O (26.8mmo1, 9.5g) was put into the reaction system, and 600mL of ethylene glycol ethyl ether and 200mL of ethylene glycol were addedRefluxing a mixed solution of mL purified water for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, carrying out suction filtration on the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence to obtain a red powdered bridging ligand B-057(11.6g, the yield is 60%);
2) weighing the intermediate B-057(8mmol, 11.6g), adding a ligand acetylacetone C-057(24mmol, 5.1g), adding 240mL of ethylene glycol ethyl ether and 11g of potassium carbonate into the system, stirring at 120 ℃ for 24 hours under the protection of nitrogen, carrying out suction filtration, alcohol washing, petroleum ether washing, drying, using dichloromethane as a solvent, carrying out silica gel column chromatography, concentrating the filtrate, and precipitating a solid to obtain a final red compound L057(4.2g, the yield is 29.2%);
HPLC purity is more than 99.5 percent;
mass spectrum calculated 898.18; test value 898.20;
elemental analysis calculated C: 62.85%; 5.95 percent of H; 6.24 percent of N; 3.56 percent of O; 21.40 percent of Ir; (ii) a The test value is C: 62.81%; 5.98 percent of H; 6.25 percent of N; 3.59 percent of O; 21.45 percent of Ir.
Specifically, the reaction formulae of steps 1) to 2) are as follows:
in the embodiment, the iridium metal complex is applied to preparation of organic electroluminescent device products.
Example 4
An iridium metal complex L076, namely a compound with the number of L076, comprises the following specific synthetic steps:
1) weighing A-076(70.8mmol, 20g) and IrCl under the protection of nitrogen3·3H2Placing O (23.6mmo1,8.3g) into a reaction system, adding a mixed solution of 600mL of ethylene glycol ethyl ether and 200mL of purified water, refluxing for 24 hours at 120 ℃ 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 to obtain a red-powder bridging ligand B-076(11.2g, the yield is 60.2%);
2) intermediate B-076(7.1mmo, 11.2g) was weighed, ligand C-076(21.3mmol, 5g) was added, and then ethylene glycol ethyl ether 220mL and potassium carbonate (9.8g) were added to the system, and the mixture was stirred at 120 ℃ for 24 hours under nitrogen protection, filtered, washed with alcohol, washed with petroleum ether, dried, and then dichloromethane was used as a solvent, and subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain final red compound L076(4.9g, yield 34.7%). HPLC purity is more than 99.5 percent;
mass spectrum calculated 990.24; test value 990.25;
elemental analysis calculated C: 66.71%; 4.99 percent of H; 5.66 percent of N; 3.23 percent of O; 19.41 percent of Ir; the test value is 66.70 percent of C; 5.00 percent of H; 5.65 percent of N; 3.20 percent of O; 19.41 percent of Ir.
Specifically, the reaction formulae of steps 1) to 2) are as follows:
in the embodiment, the iridium metal complex is applied to preparation of organic electroluminescent device products.
Example 5
An iridium metal complex L106, namely a compound with the number of L106, comprises the following specific synthetic steps:
1) weighing A-106(89.6mmol, 20g) and IrCl under the protection of nitrogen3·3H2Placing O (29.9mmo1, 10.6g) into a reaction system, adding a mixed solution of 600mL of ethylene glycol ethyl ether and 200mL of purified water, refluxing for 24 hours at 120 ℃ 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 to obtain a red powdered bridging ligand B-106(11.8g, the yield is 59.3%);
2) weighing the intermediate B-106(8.85mmol, 11.8g), adding the ligand C-106(26.55mmol, 4.2g), adding 240mL of ethylene glycol ethyl ether and potassium carbonate (12.2g) into the system, stirring for 24 hours at 120 ℃ under the protection of nitrogen, performing suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, performing silica gel column chromatography, and concentrating the filtrate to separate out a solid to obtain a final red compound L106(5.7g, the yield is 40.7%);
HPLC purity greater than 99.5%;
mass spectrum calculated 794.02; test value 794.0;
elemental analysis, calculated value C is 58.99 percent; 5.71 percent of H; 7.06 percent of N; 4.03 percent of O; 24.21 percent of Ir; the test value is C: 58.95%; 5.70 percent of H; 7.04 percent of N; 4.04 percent of O; 24.20 percent of Ir
Specifically, the reaction formulae of steps 1) to 2) are as follows:
in the embodiment, the iridium metal complex is applied to preparation of organic electroluminescent device products. The synthesis methods of other compounds are the same as those described above, and are not repeated herein, and the mass spectra or molecular formulas of other synthesis examples are shown in the following table:
| compound (I) | Molecular formula | Calculated mass spectrum | Mass spectrometric test values |
| L004 | C45H33IrN4O2 | 854.00 | 854.00 |
| L018 | C33H27IrN6O2 | 731.84 | 731.80 |
| L030 | C49H41IrN4O2 | 910.11 | 910.10 |
| L042 | C37H35IrN6O2 | 787.94 | 787.98 |
| L069 | C47H53IrN4O2 | 898.18 | 898.20 |
| L076 | C55H49IrN4O2 | 990.24 | 990.30 |
| L087 | C43IrN6O6 | 928.04 | 928.00 |
| L118 | C49H55D2IrN4O2 | 928.25 | 928.30 |
The present invention also provides an organic electroluminescent device made of the iridium metal complex, more particularly, the iridium metal complex represented by chemical formula 1.
Example 6
An organic electroluminescent device was prepared using the compound L001 prepared in example 1, which is more specifically:
coating with a thickness of
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. Firstly, the upper surface of ITO (anode) is evaporated with CuPc
Followed by deposition of NPB
Mixing and evaporating a main material compound H1 and a doping material compound L00195:5 in weight ratio
Evaporated electron transport layer "Alq3"
Evaporation of electron injection layer LiF
Deposition cathode Al
And (4) preparing the organic electroluminescent device. Testing the performance luminescence characteristics of the obtained device by using a KEITHLEY2400 type source measurement unit, CS-2000A spectral radiance meter is used to evaluate the drive voltage, luminance and luminous efficiency.
By referring to the method, the compound L001 is respectively replaced by L008, L017, L055 and L089, and the organic electroluminescent device of the corresponding compound is prepared.
Comparative example 1
An organic electroluminescent device was prepared in the same manner as in example 6, and the structure of the device-constituting compound was as follows:
the same examination as in example 6 was performed on the prepared organic electroluminescent device, and the results are shown in table 1.
Table 1 test results of organic electroluminescent devices in example 6 and comparative example 1
Table 1 shows that the organic electroluminescent device prepared using the iridium metal complex provided by the present invention as a luminescent layer doping material has a significantly reduced driving voltage and a significantly improved current efficiency, compared to the organic electroluminescent device prepared using the comparative compound comparative example 1 as a luminescent layer doping material.
The invention has the beneficial effects that: the iridium metal complex with the novel structure provided by the invention has the advantages that the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is reduced by driving voltage.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (11)
1. An iridium metal complex characterized by: the complex has a structure shown in chemical formula 1:
wherein: r1、R2、R3Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, or substituted or unsubstituted C8-C16 condensed ring group, R4Is substituted or unsubstituted alkane, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C4-C6 aromatic heterocyclic group.
2. An iridium metal complex according to claim 1, wherein: the R is4Is a substituted or unsubstituted alkyl group.
3. An iridium metal complex according to claim 1, wherein: the R is1、R2、R3The substitution position is any position of the ring; r1And R2The number of the substituents is 0-3, R3Number of substituentsIs 0 to 2.
4. An iridium metal complex according to claim 1, wherein: the alkyl is a straight-chain alkyl, a branched-chain alkyl, a cyclic alkyl, a straight-chain alkyl substituted by at least 1 substituent, a branched-chain alkyl substituted by at least 1 substituent or a cyclic alkyl substituted by at least 1 substituent; wherein, the substituent is one or more of halogen, deuterium, cyano and hydroxyl independently.
5. An iridium metal complex according to claim 1, wherein: the aryl group is preferably an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, deuterium, amino, cyano, nitro or hydroxy.
6. An iridium metal complex according to claim 1, wherein: the aromatic heterocyclic group is preferably an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro or hydroxy.
7. An iridium metal complex according to claim 1, wherein: the R is1、R2、R3Each independently forms a substituted or unsubstituted C3-C12 aliphatic ring, a substituted or unsubstituted C6-C12 aromatic ring, a substituted or unsubstituted C2-C12 aromatic heterocycle, a substituted or unsubstituted C6-C12 condensed ring with the ring; or R1And R2、R2And R3Form a substituted or unsubstituted C3-C12 aliphatic ring, a substituted or unsubstituted C6-C12 aromatic ring, a substituted or unsubstituted C2-C12 aromatic heterocycle, a substituted or unsubstituted C6-C12 fused ring, or a substituted or unsubstituted C5-C12 spiro ring.
8. An iridium metal complex according to claim 1, wherein: the substituent on the substituent group is at least one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C12 aryl and substituted or unsubstituted C4-C12 aromatic heterocyclic group.
9. An iridium metal complex according to claim 1, wherein: the iridium metal complex is selected from any one of the following structures:
10. a method for preparing an iridium metal complex as claimed in claim 1, comprising the steps of:
1) providing compound a and compound C, respectively, represented by the following structural formulae:
2) fully reacting the raw material A with iridium trichloride to prepare a bridging ligand intermediate B;
3) and fully reacting the intermediate B with the intermediate C to obtain the iridium metal complex shown in the chemical formula 1. The bridged ligand intermediate B has the structure:
the synthetic route is as follows:
wherein: r1、R2、R3、R4And the number of substituents of each thereof is in accordance with the range defined in chemical formula 1.
11. An electroluminescent device comprising the iridium metal complex of claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113214325A (en) * | 2020-07-15 | 2021-08-06 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex and preparation method and application thereof |
| CN114075252A (en) * | 2021-08-25 | 2022-02-22 | 吉林奥来德光电材料股份有限公司 | Iridium metal compound, light-emitting material, light-emitting layer, and organic electroluminescent device |
| WO2022262309A1 (en) * | 2021-06-18 | 2022-12-22 | 广东阿格蕾雅光电材料有限公司 | Organometallic iridium compound and application thereof |
| WO2023221346A1 (en) * | 2022-05-18 | 2023-11-23 | 吉林奥来德光电材料股份有限公司 | Organometallic compound and use thereof, light-emitting device and light-emitting apparatus |
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| CN111484532A (en) * | 2019-11-20 | 2020-08-04 | 吉林奥来德光电材料股份有限公司 | Phosphor luminescent material, preparation method thereof and organic electroluminescent device |
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| CN104844658A (en) * | 2014-02-18 | 2015-08-19 | 环球展览公司 | Organic electroluminescent materials and devices |
| CN111484532A (en) * | 2019-11-20 | 2020-08-04 | 吉林奥来德光电材料股份有限公司 | Phosphor luminescent material, preparation method thereof and organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113214325A (en) * | 2020-07-15 | 2021-08-06 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex and preparation method and application thereof |
| WO2022262309A1 (en) * | 2021-06-18 | 2022-12-22 | 广东阿格蕾雅光电材料有限公司 | Organometallic iridium compound and application thereof |
| CN114075252A (en) * | 2021-08-25 | 2022-02-22 | 吉林奥来德光电材料股份有限公司 | Iridium metal compound, light-emitting material, light-emitting layer, and organic electroluminescent device |
| WO2023221346A1 (en) * | 2022-05-18 | 2023-11-23 | 吉林奥来德光电材料股份有限公司 | Organometallic compound and use thereof, light-emitting device and light-emitting apparatus |
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