CN111039995A - Phosphorescent complex, preparation method thereof and organic electroluminescent device - Google Patents
Phosphorescent complex, preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a phosphorescent complex, a preparation method thereof and an organic electroluminescent device, wherein the phosphorescent complex has a structural general formula
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a phosphorescent complex, a preparation method thereof and an organic electroluminescent device.
Background
In recent years, organic electroluminescent diodes (OLEDs) have been favored because of their excellent characteristics, such as being ultra-thin, flexible, self-emissive, and wide viewing angle. At present, the efficiency and the service life of the green and yellow organic phosphorescent materials basically meet the requirements of industrial production, but high-performance red phosphorescent materials still need to be developed.
In 1963, the Pope research group applied 400V direct current to vapor-deposited micron-sized single-crystal anthracene, and under the vacuum condition, the organic electroluminescence phenomenon was observed for the first time. In 2011, Kwon research combined a red-light iridium complex, i.e. a phosphorescent complex shown in formula 1, and Bebq is adopted2The maximum emission wavelength of the electroluminescent device as a light-emitting body is 620nm, the driving voltage is only 2.4V at a low level, the CIE color coordinates are (0.64, 0.35), and the maximum current efficiency is 30.1 cd/A. In 2017, Kido researches combine a deep red phosphorescent complex, namely the phosphorescent complex shown in formula 2, and the phosphorescent complex is used as a main material to prepare an evaporation type photoelectric device, wherein the maximum emission peak position is 670nm, the driving voltage is 2.4V, and the CIE color coordinate is (0.70, 0.29);
the lack of the current high-efficiency red-light phosphorescent luminescent material always restricts the rapid development of the organic electroluminescent material. In recent years, the most used red phosphorescent materials are mainly platinum complexes, but the platinum complexes are planar structures, so that aggregation is easy to occur, and the photoelectric properties of the platinum complexes are affected. In contrast, the octahedral cyclometalated iridium complex has the characteristics of short phosphorescence life, high efficiency, simple synthesis, easy adjustment of light color and the like, and becomes a very important research direction for designing novel efficient red light phosphorescence luminescent materials at present.
Disclosure of Invention
In view of the above, the present invention provides a phosphorescent compound, a method for preparing the same, and an organic electroluminescent device, wherein the phosphorescent compound is applied to the electroluminescent device, and the organic electroluminescent device prepared by using the phosphorescent compound has high current efficiency, low driving voltage, and long phosphorescent lifetime.
In order to achieve the purpose, the invention adopts the following technical scheme:
a phosphorescent complex has a structure shown as formula G:
wherein:
R1～R5each independently represents hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid group, ester group, nitrile group, isonitrile group, thio group, sulfinyl group, sulfonyl group, phosphino group; or said R1～R6Wherein any adjacent substituents are optionally joined or fused to form a ring;
R1～R3the substituent position of (A) is any position of the ring, R1～R3The number of the substituents is 0 to 4, R4～R6The number of the substituents is 0 to 1.
Preferably, said R is1～R3Form a ring with each other between any adjacent substituents, or said R1～R3Form a ring with other substituents on the ring, and the R4～R6Any adjacent substituents form a ring with each other.
Preferably, the alkyl is a straight chain alkyl, a branched chain alkyl, a cyclic alkyl, a straight chain alkyl substituted with at least 1 substituent, a branched chain alkyl substituted with at least 1 substituent, or a cyclic alkyl substituted with at least 1 substituent, wherein the substituents are independently selected from deuterium, methyl, ethyl, isopropyl, nitro, halogen, and a combination of one or more of carboxyl.
Preferably, the aryl group is an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituent groups are independently selected from one or more of deuterium, nitro, halogen, nitrile group, methyl, isopropyl and tert-butyl.
Preferably, the heteroaryl is unsubstituted heteroaryl or heteroaryl substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is selected from one or more of nitrogen, sulfur or oxygen in combination.
Preferably, the halogen is selected from one or more of fluorine, chlorine and bromine.
Preferably, said R is1～R6The hydrogen atom in the group or substituent group of (a) is deuterated.
Preferably, the specific structural formula of the phosphorescent complex shown in chemical formula 1 is:
some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of the groups and the substituted groups and substituted positions thereof, which is not described in detail herein.
The invention also provides a preparation method of the phosphorescent complex, which comprises the following steps:
s1, dissolving iridium trichloride of a compound shown as a formula A in ethylene glycol ethyl ether and water, carrying out reflux reaction for 20-36h under the protection of inert gas, and after the reaction is finished, cooling, precipitating, filtering, washing and drying to obtain a bridged ligand compound shown as a formula B;
s2, sequentially adding the bridged ligand compound shown in the formula B, the diketone derivative shown in the formula C, anhydrous potassium carbonate and ethylene glycol ethyl ether into a three-necked bottle, carrying out reflux reaction under the protection of inert gas for 20-36h, and after the reaction is finished, cooling, precipitating, carrying out suction filtration, washing, drying, carrying out column chromatography and concentrating to obtain the phosphorescent complex shown in the formula G;
the synthesis route of the phosphorescent complex is as follows:
preferably, in step S1, the reaction molar ratio of the compound represented by formula a to iridium trichloride is 2.5: 1.
Preferably, in the step S2, the reaction molar ratio of the bridged ligand compound represented by the formula B to the diketone derivative represented by the formula C is 1: 3.
Preferably, in the step S1, the reaction temperature is 110-125 ℃.
Preferably, in the step S2, the reaction temperature is 110-125 ℃.
Preferably, in step S1, the post-processing procedure is: and cooling to room temperature, separating out a precipitate, performing vacuum filtration, sequentially leaching with absolute ethyl alcohol and petroleum ether, and drying to obtain the bridged ligand compound shown in the formula B.
Preferably, in step S2, the post-processing procedure is: cooling to room temperature, carrying out vacuum filtration, leaching a filter cake with ethanol, drying under-0.1 Mpa at 50 ℃, passing through a silica gel column, and spin-drying the obtained filtrate to obtain the phosphorescent complex shown in the formula G.
Preferably, the diketone derivative represented by the formula C is selected from the following compounds:
the invention further provides the application of the phosphorescent complex in an organic electroluminescent device.
The invention also provides an organic electroluminescent device containing the phosphorescent complex.
The organic electroluminescent device includes: a first electrode, a second electrode and at least one organic layer, said organic layer being located between said first electrode and said second electrode and at least one of said organic layers comprising a phosphorescent complex according to any one of claims 1 to 7; the phosphorescent complex exists in the organic layer in a single form or in a mixture with other substances.
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 organic electroluminescent device includes a light-emitting layer containing the above-described phosphorescent complex.
Preferably, the light-emitting layer includes a host material and a dopant material, the host material includes a fluorescent host and a phosphorescent host, and the dopant material is the phosphorescent complex.
Preferably, the mixing ratio of the host material to the dopant material is (90:10) - (99.5: 0.5).
The invention further provides application of the organic electroluminescent device in an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
According to the technical scheme, compared with the prior art, the invention provides the phosphorescent complex, the preparation method thereof and the organic electroluminescent device, and the phosphorescent complex has the following beneficial effects:
(1) the invention provides a phosphorescence complex with a novel structure, and an organic electroluminescent device prepared by using the phosphorescence complex has higher current efficiency, low driving voltage and longer phosphorescence service life.
(2) The preparation method of the phosphorescent complex provided by the invention has the advantages of simple and efficient 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, and it is obvious 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
The synthesis of the compound G002 comprises the following specific steps:
s1, weighing A-002(55.68mmol, 15.00g) and IrCl3·3H2O (22.28mmol, 7.80g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24h under protection, then cooling to room temperature, separating out precipitate, performing vacuum filtration, sequentially leaching with anhydrous ethanol and petroleum ether, and oven drying to obtain B-002(8.5mmol, 13.00g) with a yield of 76.5%.
S2, weighing B-002(8.50mmol, 13.00g), K2CO3(85.02mmol, 11.75g), ethylene glycolEther (100mL) was added to the reaction system separately under N2Adding C-002(3, 7-diethyl-4, 6-nonanedione) (25.5mmol, 5.41G) under protection, heating and refluxing for 24h, cooling to room temperature, carrying out suction filtration under reduced pressure, leaching a filter cake with ethanol, drying the filter cake under the conditions of-0.1 Mpa and 50 ℃, passing through a silica gel column, and carrying out spin drying on the obtained filtrate to obtain G-002(10.52mmol, 9.90G) with the yield of 61.9%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 940.22; test value 940.36.
Elemental analysis:
theoretical value C, 67.71%; h, 5.47%; ir, 20.44%; n, 2.98%; o, 3.40%;
test value C, 67.73%; h, 5.49%; ir, 20.44%; n, 2.96%; o,3.41 percent.
Example 2
The synthesis of the compound G-007 comprises the following specific steps:
s1, weighing A-007(50.43mmol, 15.00g) and IrCl3·3H2O (20.17mmol, 7.11g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24h under protection, then cooling to room temperature, separating out precipitate, performing vacuum filtration, sequentially leaching with anhydrous ethanol and petroleum ether, and oven drying to obtain B-007(7.31mmol, 12.00g) with a yield of 72.4%.
S2, weighing B-007(7.31mmol, 12.00g), K2CO3(73.08mmol, 10.10g) and ethylene glycol ethyl ether (100mL) were added to the reaction system separately in N2Adding C-007(3, 7-diethyl-4, 6-nonanedione) (21.93mmol, 4.64G) under protection, heating and refluxing for 24h, cooling to room temperature, carrying out suction filtration under reduced pressure, leaching a filter cake with ethanol, drying the filter cake under the conditions of-0.1 Mpa and 50 ℃, passing through a silica gel column, and carrying out spin drying on the obtained filtrate to obtain G-007(8.02mmol, 8.01G) with the yield of 54.9%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 996.33; test value 996.42.
Elemental analysis:
theoretical value C, 68.72%; h, 5.97%; ir, 19.29%; n, 2.81%; o, 3.21%;
test value C, 68.73%; h,5.99 percent; ir, 19.28%; n, 2.80%; and 3.23 percent of O.
Example 3
The synthesis of the compound G-050 comprises the following specific steps:
s1, weighing A-050(47.56mmol, 15.00g) and IrCl3·3H2O (19.02mmol, 6.71g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24h under protection, then cooling to room temperature, separating out precipitate, performing vacuum filtration, sequentially leaching with anhydrous ethanol and petroleum ether, and oven drying to obtain B-050(6.97mmol, 12.00g) with a yield of 75.1%.
S2, weighing B-050(6.97mmol, 12.00g), K2CO3(69.68mmol, 9.63g) and ethylene glycol ethyl ether (100mL) were added to the reaction system separately in N2Adding C-050(3, 7-diethyl-4, 6-nonanedione) (20.91mmol, 4.43G) under protection, heating and refluxing for 24h, cooling to room temperature, carrying out suction filtration under reduced pressure, leaching a filter cake with ethanol, drying the filter cake under the conditions of-0.1 Mpa and 50 ℃, passing through a silica gel column, and carrying out spin drying on the obtained filtrate to obtain G-050(7.26mmol, 7.50G) with the yield of 52.1%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 1032.31; test value 1032.40.
Elemental analysis:
theoretical value C, 66.32%; h, 5.57%; f, 3.68%; ir, 18.62%; n, 2.71%; o, 3.10%;
test value C, 66.30%; h, 5.54%; f, 3.67%; ir, 18.61%; n, 2.73%; and 3.11 percent of O.
Example 4
The synthesis of the compound G-070 comprises the following specific steps:
s1, weighing A-070(43.80mmol, 15.00g) and IrCl3·3H2O (17.52mmol, 6.18g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24h under protection, then cooling to room temperature, separating out precipitate, performing vacuum filtration, sequentially leaching with anhydrous ethanol and petroleum ether, and oven drying to obtain B-070(5.49mmol, 10.00g) with a yield of 64.57%.
S2, weighing B-070(5.49mmol, 10.00g), K2CO3(54.84mmol, 7.58g) and ethylene glycol ethyl ether (100mL) were added to the reaction system separately in N2Adding C-070(2,4, 6-trimethyl-3, 5-heptanedione) (16.47mmol, 2.77G) under protection, heating and refluxing for 24h, cooling to room temperature, vacuum filtering, leaching a filter cake with ethanol, drying under the conditions of-0.1 Mpa and 50 ℃, passing through a silica gel column, and spin-drying the obtained filtrate to obtain G-070(5.45mmol, 5.70G) with the yield of 49.7%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 1044.24; test value 1044.34.
Elemental analysis:
theoretical value C, 62.11%; h, 4.92%; ir, 18.41%; n, 5.37%; o, 9.19%;
test value C, 62.14%; h, 4.95%; ir, 18.41%; n, 5.36%; and O,9.21 percent.
Example 5
The synthesis of the compound G-093 comprises the following specific steps:
s1, weighing A-093(39.86mmol, 15.00g) and IrCl3·3H2O (15.94mmol, 5.62g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24 hr under protection, cooling to room temperature to precipitate, vacuum filtering, and purifying with anhydrousEthanol and petroleum ether were sequentially eluted and dried to give B-093(5.93mmol, 11.00g) in 74% yield.
S2, weighing B-093(5.93mmol, 11.00g), K2CO3(59.33mmol, 8.2g) and ethylene glycol ethyl ether (100mL) were added to the reaction system separately in N2Adding C-093(1, 5-diphenyl-2, 4-pentanedione) (17.79mmol, 3.95G) under protection, heating and refluxing to 120 ℃, cooling to room temperature, vacuum filtering, leaching a filter cake with ethanol, drying under-0.1 Mpa at 50 ℃, passing through a silica gel column, and spin-drying the obtained filtrate to obtain G-093(6.17mmol, 7.20G) with a yield of 52.1%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 1166.05; test value 1166.13.
Elemental analysis:
theoretical value C, 60.77%; h, 3.89%; br, 13.71%; ir, 16.48%; n, 2.40%; o, 2.74%;
test value C, 60.74%; h, 3.83%; br, 13.70%; ir, 16.46%; n, 2.41%; o,2.73 percent.
Example 6
The synthesis of the compound G-097 comprises the following specific steps:
s1, weighing A-097(45.26mmol, 15.00g) and IrCl3·3H2O (18.10mmol, 6.38g), ethylene glycol ethyl ether (300mL), and water (100mL) were added to the reaction system, respectively, under N2Heating and refluxing for 24h under protection, then cooling to room temperature, separating out precipitate, performing vacuum filtration, sequentially leaching with anhydrous ethanol and petroleum ether, and oven drying to obtain B-097(6.78mmol, 12.05g) with a yield of 74.6%.
S2, weigh B-004(6.75mmol, 12.00g), K2CO3(67.51mmol, 9.33g) and ethylene glycol ethyl ether (100mL) were added to the reaction system, respectively, under N2Adding C-097(3, 7-diethyl-4, 6-nonanedione) (20.25mmol, 4.29g) under protection, heating to 120 deg.C, refluxing for 24h, and cooling to room temperatureVacuum filtering, leaching the filter cake with ethanol, oven drying at-0.1 Mpa and 50 deg.C, passing through silica gel column, and spin drying the obtained filtrate to obtain G-097(6.12mmol, 6.51G) with yield of 45.2%.
HPLC purity: 99 percent.
Mass spectrum: theoretical value 1064.30; test value 1064.37.
Elemental analysis:
theoretical value C, 62.07%; h, 5.59%; ir, 18.06%; n, 5.26%; o, 9.02%;
test value C, 62.08%; h,5.60 percent; ir, 18.07%; n, 5.27%; and O,9.03 percent.
Examples 7 to 21
The target compounds of examples 7 to 21 can be synthesized by the synthesis method of example 1 by replacing the corresponding reactants, and the specific structural chemical formulas and the results of MS (i.e., mass spectrum) are shown in table 1.
TABLE 1 chemical formulas of target compounds of examples 7 to 16 and MS results
Example 22
The embodiment provides an organic electroluminescent device, which comprises a substrate, an anode layer arranged on the substrate, a hole injection layer arranged on the anode layer, a hole transport layer arranged on the hole injection layer, an organic light emitting layer arranged on the hole transport layer, an electron transport layer arranged on the organic light emitting layer, an electron injection layer arranged on the electron transport layer and a cathode layer arranged on the electron injection layer.
The preparation method of the organic electroluminescent device comprises the following steps:
coating with a thickness of
The ITO glass substrate is put in distilled water to be cleaned for 2 times,ultrasonic cleaning for 30 minutes, repeatedly cleaning with distilled water for 2 times, ultrasonic cleaning for 15 minutes, after the cleaning with distilled water is finished, sequentially ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, methanol, etc., drying, transferring to a plasma cleaning machine, cleaning the substrate for 5 minutes, and transferring to a deposition machine. Firstly, the upper surface of ITO (anode) is evaporated with CuPc
Followed by deposition of NPB
Host substance 4,4'-N, N' -biphenyl dicarbazole ('CBP') and doping substance compound G-002 are mixed for evaporation
Wherein the weight ratio of CBP to dopant compound G-002 is 95: 5; vapor deposition of electron transport layer Alq3"
Evaporation of electron injection layer LiF
Deposition cathode Al
The organic electroluminescent device is prepared in the form of.
By referring to the method, G002 is respectively replaced by G-001, G-007, G-010, G-013, G-026, G-035, G-041, G-045, G-050, G-052, G-055, G-063, G-070, G-075, G-080, G-086, G-090, G-093, G-097 and G-100, and the organic electroluminescent devices of the corresponding compounds are prepared.
Comparative example 1
An organic electroluminescent device was fabricated in the same manner as in example 22, except that the dopant compound G002 of the organic light-emitting layer was replaced with the compound Ir (bty)2(acac), organic electroluminescent device obtained, Compound Ir (bty)2The structural formula of (acac) is shown below:
to further illustrate the luminescence properties of the novel iridium complex as a phosphorescent material, the devices obtained in example 22 and comparative example 1 were tested for their luminescence properties, and the results of driving voltage, luminescence brightness, and luminescence efficiency were evaluated using a KEITHLEY model 2400 source measuring unit, a CS-2000 spectroradiometer, and are shown in table 2.
Table 2 test results of organic electroluminescent devices in example 22 and comparative example 1
As can be seen from Table 2, the light-emitting luminance was 4000cd/cm2Compared with a comparative example 1, the driving voltage of the device provided by the invention is 3.92-4.56V, which is obviously lower than that of the comparative example 1, the efficiency (34.6-42.1) is far higher than that of the comparative example 1, and the service life (641-745) is 4-5 times that of the comparative example 1, so that the organic electroluminescent device prepared by using the phosphorescent complex provided by the invention as a luminescent layer material is superior to the organic electroluminescent device of the comparative phosphorescent complex, the driving voltage is obviously reduced, the current efficiency is obviously improved, and the phosphorescent service life is obviously improved.
It will be apparent to those skilled in the art that many modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. It is therefore contemplated that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A phosphorescent complex is characterized in that the structure of the phosphorescent complex is shown as formula G:
wherein:
R1～R6each independently represents hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid group, ester group, nitrile group, isonitrile group, thio group, sulfinyl group, sulfonyl group, phosphino group;
R1～R3the substituent position of (A) is any position of the ring, R1～R3The number of the substituents is 0 to 4, R4～R6The number of the substituents is 0 to 1.
2. The phosphorescent complex of claim 1, wherein R is1～R3Form a ring with each other between any adjacent substituents, or said R1～R3Form a ring with other substituents on the ring, and the R4～R6Any adjacent substituents form a ring with each other.
3. The phosphorescent complex of claim 1, wherein the alkyl group is a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkyl group substituted with at least 1 substituent, a branched alkyl group substituted with at least 1 substituent, or a cyclic alkyl group substituted with at least 1 substituent, wherein the substituents are independently selected from deuterium, methyl, ethyl, isopropyl, nitro, halogen, and a combination of one or more of carboxyl groups.
4. A phosphorescent complex according to claim 1, wherein the aryl group is an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituent groups are independently selected from one or more of deuterium, nitro, halogen, nitrile group, methyl, isopropyl and tert-butyl.
5. The phosphorescent complex of claim 1, wherein the heteroaryl group is an unsubstituted heteroaryl group or a heteroaryl group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is selected from one or more of nitrogen, sulfur or oxygen in combination.
6. A phosphorescent complex according to claim 1 wherein the halogen is selected from the group consisting of fluorine, chlorine and bromine.
7. A phosphorescent complex according to any one of claims 1 to 6 wherein R is1～R6The hydrogen atom in the group or substituent group of (a) is deuterated.
8. A method for preparing a phosphorescent complex according to any one of claims 1 to 7, comprising the steps of:
s1, dissolving the compound shown in the formula A and iridium trichloride into a mixed solution of ethylene glycol ethyl ether and water, carrying out reflux reaction for 20-36h under the protection of inert gas, and after the reaction is finished, cooling, precipitating, carrying out suction filtration, washing and drying to obtain a bridged ligand compound shown in the formula B;
s2, sequentially adding the bridged ligand compound shown in the formula B, the diketone derivative shown in the formula C, anhydrous potassium carbonate and ethylene glycol ethyl ether into a three-necked bottle, carrying out reflux reaction under the protection of inert gas for 20-36h, and after the reaction is finished, cooling, precipitating, carrying out suction filtration, washing, drying, carrying out column chromatography and concentrating to obtain the phosphorescent complex shown in the formula G;
the synthesis route of the phosphorescent complex is as follows:
9. use of a phosphorescent complex according to any one of claims 1 to 7 in an organic electroluminescent device.
10. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer, wherein the organic layer is located between the first electrode and the second electrode, and wherein at least one of the organic layers comprises the phosphorescent complex of any one of claims 1 to 7; the phosphorescent complex exists in the organic layer in a single form or in a mixture with other substances.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818741A (en) * | 2019-11-15 | 2020-02-21 | 吉林奥来德光电材料股份有限公司 | Organic doped luminescent compound, preparation method thereof and organic electroluminescent device |
| 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 |
| CN113387983A (en) * | 2020-03-11 | 2021-09-14 | 北京夏禾科技有限公司 | Metal complex of ligand with polysubstituted biaryl structure |
| CN116789709A (en) * | 2023-06-25 | 2023-09-22 | 新疆医科大学 | Organometallic complex and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040239237A1 (en) * | 2001-06-04 | 2004-12-02 | Noriyuki Matsusue | Organic electroluminescent element, luminiscent material and organic compound |
-
2019
- 2019-12-27 CN CN201911377513.3A patent/CN111039995A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040239237A1 (en) * | 2001-06-04 | 2004-12-02 | Noriyuki Matsusue | Organic electroluminescent element, luminiscent material and organic compound |
Non-Patent Citations (2)
| Title |
|---|
| MANLI HUANG等: "Highly Efficient Solution-Processed Deep-Red Organic Light-Emitting Diodes Based on an Exciplex Host Composed of a Hole Transporter and a Bipolar Host", 《J. PHYS. CHEM. LETT.》 * |
| YOUNG HEE LEE等: "Theoretical Study of Ir(III) Complexes of Fluorinated Phenylbenzoquinoline as Red Phosphorescent Material", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818741A (en) * | 2019-11-15 | 2020-02-21 | 吉林奥来德光电材料股份有限公司 | Organic doped luminescent compound, preparation method thereof and organic electroluminescent device |
| CN113387983A (en) * | 2020-03-11 | 2021-09-14 | 北京夏禾科技有限公司 | Metal complex of ligand with polysubstituted biaryl structure |
| CN113387983B (en) * | 2020-03-11 | 2023-04-18 | 北京夏禾科技有限公司 | Metal complex of ligand with polysubstituted biaryl structure |
| 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 |
| CN116789709A (en) * | 2023-06-25 | 2023-09-22 | 新疆医科大学 | Organometallic complex and preparation method and application thereof |
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