CN110790797A - Organic phosphorus luminescent material and preparation method and application thereof - Google Patents
Organic phosphorus luminescent material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110790797A CN110790797A CN201911090336.0A CN201911090336A CN110790797A CN 110790797 A CN110790797 A CN 110790797A CN 201911090336 A CN201911090336 A CN 201911090336A CN 110790797 A CN110790797 A CN 110790797A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- compound
- luminescent material
- organic phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 7
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims abstract description 5
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims abstract description 5
- 125000006746 (C1-C60) alkoxy group Chemical group 0.000 claims abstract description 3
- 125000006744 (C2-C60) alkenyl group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- -1 nitro, hydroxyl Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims abstract description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 65
- 150000001875 compounds Chemical class 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004587 chromatography analysis Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000006745 (C2-C60) alkynyl group Chemical group 0.000 claims description 2
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 description 21
- 238000001914 filtration Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- MFELLNQJMHCAKI-UHFFFAOYSA-N 3,7-diethylnonane-4,6-dione Chemical compound CCC(CC)C(=O)CC(=O)C(CC)CC MFELLNQJMHCAKI-UHFFFAOYSA-N 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 238000011056 performance test Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses an organic phosphorus luminescent material, which has a molecular structure general formula as follows:
R1、R2、R3、R4、R5and R6All are hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstitutedAnd X is O or S, the organic electroluminescent device prepared by using the same has excellent color purity and brightness and prolonged durability.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic phosphorus luminescent material and a preparation method and application thereof.
Background
The Organic Light Emitting Diode (OLED) has the advantages of being thin and light, actively emitting light, wide in viewing angle, fast in response, low in energy consumption, excellent in low temperature and anti-seismic performance, and potentially flexible in design, and the like.
The light emitting material of the organic light emitting diode is mainly a phosphorescent light emitting material, and independent light emission of three primary colors of red, blue, and green among them is currently the most adopted color mode, as the light emitting material, excitons are formed by recombination of electrons and holes injected from each electrode, singlet excitons emit fluorescence, triplet excitons emit phosphorescence, the emission singlet excitons have a formation probability of 25%, and the triplet excitons emitting phosphorescence have a formation probability of 75%, and thus, the triplet excitons provide greater light emitting efficiency than the singlet excitons, and in such a phosphorescent material, the red phosphorescent material can have greater light emitting efficiency than the fluorescent material. Currently, as an important factor for improving the efficiency of organic electroluminescent devices, red phosphorescent materials are being widely studied.
However, the presently disclosed luminescent materials, especially red luminescent materials, have certain deficiencies in both luminous efficiency and thermal stability. Therefore, the development of an organic phosphorus luminescent material with high luminescent efficiency and good thermal stability is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides an organic phosphorus luminescent material with high luminescent efficiency and good thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses an organic phosphorus luminescent material, which has a molecular structure general formula as follows:
wherein: r1、R2、R3、R4、R5And R6All are any one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C5-C60 heterocyclic group, substituted or unsubstituted C10-C60 condensed ring group and substituted or unsubstituted C5-C60 spiro ring group;
x is O or S;
wherein, in the formula (I), R1, R2 and R3 represent any positions of a ring, R1 and R3 represent single, two, three or no substituent, R2 and R5 represent single, two or no substituent, and R4 and R6 represent single or no substituent.
Further, any adjacent R mentioned above1、R2、R3The substituent forms a condensed ring or aromatic heterocyclic ring with the ring, and R of the condensed ring or aromatic heterocyclic ring is not formed1、R2Or R3Is hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C5-C60 heterocyclic group,Any one of a substituted or unsubstituted C10-C60 condensed ring group and a substituted or unsubstituted C5-C60 spiro ring group.
Further, the above R1、R2、R3、R4、R5And R6Is any one of hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C5-C30 heterocyclic group, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C10-C30 condensed ring group, and X is O.
Further, the organic phosphorus luminescent material has a structural formula of any one of I-1 to I-70:
the invention also provides a preparation method of the organic phosphorus luminescent material, which comprises the following steps:
1) weighing a compound (II) and iridium trichloride under a nitrogen protection system, putting the compound (II) and iridium trichloride into a reaction system, adding a solvent 1, reacting under the nitrogen protection system, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and sequentially washing and drying the precipitate with water, absolute ethyl alcohol and petroleum ether to obtain a compound (IV);
2) weighing the compound (IV) obtained in the step 1), adding alkali, adding a solvent 2 into the system, replacing nitrogen for three times, adding the compound (III) under the protection of nitrogen for reaction, cooling, carrying out suction filtration, washing with alcohol, drying, adding dichloromethane, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to finally obtain the organophosphorus luminescent material;
the structural formulas of the compound (II), the compound (III) and the compound (IV) are respectively as follows:
further, in the step 1), the molar ratio of the compound (II) to the iridium trichloride is (2.2-2.5): 1.
Further, in the step 1), the solvent 1 is a mixed solution of ethylene glycol ether and ultrapure water, the volume ratio of the ethylene glycol ether to the ultrapure water is 3:1, and the amount of the solvent 1 is 15-30 times of the mass of the iridium trichloride.
Further, the reaction time in step 1) is 24 to 30 hours.
Further, in the step 2), the molar ratio of the compound (IV) to the compound (III) is 1 (2.5-8), the alkali is anhydrous potassium carbonate or anhydrous sodium carbonate, and the amount of the alkali is 8-15 times of the mass of the compound (IV).
The solvent 2 is ethylene glycol ethyl ether, the amount of the solvent 2 is 10 to 30 times of the mass of the compound (IV), the reaction time is 10 to 30 hours, preferably 20 to 24 hours, and the amount of the dichloromethane is 10 to 100 times of the mass of the compound (IV).
The invention also provides the application of the organic phosphorus luminescent material in preparing organic electroluminescent devices.
The invention has the beneficial effects that: the organic phosphorus luminescent material has lower voltage and obviously improved current efficiency, and the organic electroluminescent device prepared by the organic electroluminescent device luminescent layer has excellent color purity and brightness and prolonged durability.
Detailed description of the preferred embodiments
The following examples are intended to illustrate the present invention, but are not intended to limit the present invention. 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 compound I-1 is prepared by the following specific synthetic steps:
weighing ligand II-124 mmol and IrCl under the protection of nitrogen3·3H2Adding O10 mmol into a reaction system, adding a mixed solution of 180ml of ethylene glycol ethyl ether and 60ml of ultrapure water, refluxing for 25 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence to obtain a dark red powder of the bridging ligand IV-1 with the mass of 4.26g and the yield of 59%.
Then weighing bridging ligand IV-12.5 mmol, adding anhydrous potassium carbonate 25mmol, adding 72ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 7.5mmol under the protection of nitrogen, refluxing for 24 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain a red organic phosphorus luminescent material shown as I-1, wherein the mass of the red organic phosphorus luminescent material is 2.7 g. The yield is 60%, and the HPLC purity is more than 99.5%.
Mass spectrum calculated 897.32; the test value was 897.11.
Elemental analysis calculated as C62.92; h is 5.39; 21.43 parts of Ir; n is 3.12; o is 7.13; test value C: 62.90; h is 5.41; 21.43 parts of Ir; n is 3.10; o is 7.15.
Example 2
The compound I-21 is prepared by the following specific synthetic steps:
weighing ligand II-2125 mmol and IrCl under the protection of nitrogen3·3H2Adding O10 mmol into a reaction system, adding a mixed solution of 210ml of ethylene glycol ethyl ether and 70ml of ultrapure water, refluxing for 30 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridging ligand IV-21 was obtained as a dark red powder in a mass of 5.6g with a yield of 63%.
Then weighing bridging ligand IV-213 mmol, adding anhydrous potassium carbonate 30mmol, adding 60ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12mmol under the protection of nitrogen, refluxing for 24 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in I-21, wherein the mass of the red organic phosphorus luminescent material is 4.6 g. The yield was 75% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1037.48; the test value was 1037.59.
Elemental analysis calculated as C: 65.99; h is 6.61; 18.53 parts of Ir; 2.70 of N; o is 6.17; test value C: 65.97; h is 6.59; 18.54 parts of Ir; 2.71 of N; o: 6.19.
example 3
The compound I-27 was prepared by the following specific synthetic procedure:
weighing ligand II-2724 mmol and IrCl under the protection of nitrogen3·3H2O10 mmol is put into a reaction system, and a mixed solution of 210ml of ethylene glycol ethyl ether and 70ml of ultrapure water is addedRefluxing the solution for 30 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and washing and drying the precipitate by using water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand IV-27 was obtained as a dark red powder in a mass of 5.5g with a yield of 66%.
Then weighing bridging ligand IV-273 mmol, adding anhydrous potassium carbonate 30mmol, adding 60ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12mmol under the protection of nitrogen, refluxing for 24 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in the formula I-27, wherein the mass of the red organic phosphorus luminescent material is 4.2 g. The yield was 71% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 995.43 test 995.49.
Elemental analysis, calculated value is C65.16; h is 6.28; 19.31 parts of Ir; n is 2.81; o is 6.43; the test value is C: 65.15; h is 6.29; 19.30 parts of Ir; 2.80 of N; o is 6.45.
Example 4
The compound I-36 is prepared by the following specific synthetic steps:
weighing ligand II-3622 mmol and IrCl under the protection of nitrogen3·3H2Adding O10 mmol into a reaction system, adding a mixed solution of 120ml of ethylene glycol ethyl ether and 40ml of ultrapure water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand IV-36 was obtained as a dark red powder in a mass of 4.1g with a yield of 51%.
Then weighing bridging ligand IV-362.5 mmol, adding anhydrous potassium carbonate 25mmol, adding ethylene glycol ethyl ether 30ml into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12.5mmol under the protection of nitrogen, refluxing for 20 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in I-36, wherein the mass of the red organic phosphorus luminescent material is 2.9 g. The yield is 60%, and the HPLC purity is more than 99.5%.
Mass spectrum: calculated value 977.54; the test value was 977.32.
Elemental analysis calculated as C62.67; h is 8.25; 19.67 parts of Ir; 2.87 parts of N; o is 6.55; test value C62.69; h is 8.27; 19.65 parts of Ir; 2.86 of N; o is 6.54.
Example 5
The compound I-39 is prepared by the following specific synthetic steps:
weighing ligand II-3923 mmol and IrCl under the protection of nitrogen3·3H2Adding O10 mmol into a reaction system, adding a mixed solution of 120ml of ethylene glycol ethyl ether and 40ml of ultrapure water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridging ligand IV-39 was obtained as a dark red powder in a mass of 4.6g with a yield of 54%.
Then weighing bridging ligand IV-392.5 mmol, adding anhydrous potassium carbonate 25mmol, adding ethylene glycol ethyl ether 30ml into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12.5mmol under the protection of nitrogen, refluxing for 20 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in I-39, wherein the mass of the red organic phosphorus luminescent material is 3.3 g. The yield was 63% and the HPLC purity was greater than 99.5%.
Mass spectrum: calculated value 1033.45; the test value was 1033.41.
Elemental analysis calculated as C: 66.25; h is 6.24; 18.60 parts of Ir; 2.71 of N; o is 6.19; test value C: 66.23; h is 6.23; 18.61 parts of Ir; 2.73 parts of N; o is 6.19.
Example 6
The compound I-64 is prepared by the following specific synthetic steps:
weighing ligand II-6425 mmol and IrCl under the protection of nitrogen3·3H2And (3) adding O10 mmol into a reaction system, adding a mixed solution of 225ml of ethylene glycol ethyl ether and 75ml of ultrapure water, refluxing for 28 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and sequentially washing and drying with water, absolute ethyl alcohol and petroleum ether. The mass of the bridged ligand IV-64 obtained was 5.7g as a dark red powder, with a yield of 69%.
Then weighing bridging ligand IV-643 mmol, adding anhydrous potassium carbonate 30mmol, adding 90ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 15mmol under the protection of nitrogen, refluxing for 20 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown as I-64, wherein the mass of the red organic phosphorus luminescent material is 4.7 g. The yield was 77% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1009.45 test 1009.49.
Elemental analysis calculated as C: 65.45; h is 6.39; 19.04 parts of Ir; 2.78 of N; o is 6.34; the test value is C: 65.43; h is 6.38; 19.05 parts of Ir; n is 2.79; o is 6.35.
Example 7
The compound I-70 is prepared by the following specific synthetic steps:
weighing ligand II-7025 mmol and IrCl under the protection of nitrogen3·3H2And (3) adding O10 mmol into a reaction system, adding a mixed solution of 225ml of ethylene glycol ethyl ether and 75ml of ultrapure water, refluxing for 28 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, filtering the precipitate, and sequentially washing and drying with water, absolute ethyl alcohol and petroleum ether. The bridged ligand IV-70 was obtained as a dark red powder in a mass of 5.0g with a yield of 63%.
Then weighing bridging ligand IV-703 mmol, adding anhydrous potassium carbonate 30mmol, adding 90ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 18mmol under the protection of nitrogen, refluxing for 20 hours, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown as I-70, wherein the mass of the red organic phosphorus luminescent material is 4.6 g. The yield was 79% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 977.54 test 977.58.
Elemental analysis calculated as C62.67; h is 8.25; 19.67 parts of Ir; 2.87 parts of N; o is 6.55; test value C: 62.65; h is 8.23; 19.68 parts of Ir; 2.88 of N; o is 6.57.
Example 8
An organic electroluminescent device was prepared using the organic phosphorus luminescent material i-1 prepared in example 1, and the specific steps were:
coating with a thickness of
The ITO glass substrate is put in distilled water for cleaning for 2 times, then ultrasonic cleaning is carried out for 30 minutes, then the ITO glass substrate is cleaned for 2 times by distilled water, finally ultrasonic cleaning is carried out for 10 minutes, after the cleaning by distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and then dried, the ITO glass substrate is transferred into a plasma cleaning machine, the substrate is cleaned for 5 minutes, and the substrate is sent into an evaporation machine. Under vacuum conditions, the standard pressure was set at 1X 10-6And (4) supporting. Thereafter, the ITO substrate was coated with CuPc
NPB
CBP+Ⅰ-1(5％)Alq3LiFAnd Al
The sequence of (a) and (b) forming layers of organic material.
Example 9
An organic electroluminescent device was prepared in the same manner as in example 8 using the compounds I to 21 prepared in example 2.
Example 10
An organic electroluminescent device was prepared in the same manner as in example 8 using the compounds I to 27 prepared in example 3.
Example 11
Organic electroluminescent devices were prepared in the same manner as in example 8 using compounds I to 36 prepared in example 4.
Example 12
An organic electroluminescent device was prepared in the same manner as in example 8 using the compounds I to 39 prepared in example 5.
Example 13
An organic electroluminescent device was prepared in the same manner as in example 8 using the compounds I to 64 prepared in example 6.
Example 14
Organic electroluminescent devices were prepared in the same manner as in example 8 using the compounds I to 70 prepared in example 7.
Comparative example 1
An organic electroluminescent device was fabricated in the same manner as in example 8, except that the red light-doping compound of the light-emitting layer was (btp)2Ir (acac).
Among them, the compounds used in the embodiments of the present invention, copper phthalocyanine (CuPc), NPB, (btp)2Ir(acac)，Alq3And the structural formula of CBP is as follows:
the organic electroluminescent devices prepared in examples 8 to 14 and comparative example 1 were subjected to performance tests, and the results are shown in table 1.
TABLE 1 tables showing the results of examining the properties of the organic electroluminescent devices prepared in examples 8 to 14 and comparative example 1
As shown in Table 1, the organic phosphorus luminescent material of the present invention has a lower voltage and a significantly improved current efficiency under the same current. The organic electroluminescent device prepared by using the compound obtained by the invention as a light emitting layer of the organic electroluminescent device has excellent color purity and brightness and prolonged durability.
The organic phosphorus luminescent material is a quinoline structure oxygen atom-containing metal iridium complex, and I-1 to I-70 only list some specific structural forms, but the series of compounds are not limited to the molecular structure, and other specific molecular structures can be obtained through simple conversion of some simple groups, substituted groups and substituted positions thereof.
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. An organic phosphorus luminescent material, wherein the molecular structural general formula of the organic phosphorus luminescent material is:
wherein: r1、R2、R3、R4、R5And R6All are any one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C5-C60 heterocyclic group, substituted or unsubstituted C10-C60 condensed ring group and substituted or unsubstituted C5-C60 spiro ring group;
x is O or S;
wherein, in the formula (I), R1, R2 and R3 represent any positions of a ring, R1 and R3 represent single, two, three or no substituent, R2 and R5 represent single, two or no substituent, and R4 and R6 represent single or no substituent.
2. An organophosphorus light-emitting material according to claim 1, wherein any adjacent R is1、R2、R3The substituent forms a condensed ring or aromatic heterocyclic ring with the ring, and R of the condensed ring or aromatic heterocyclic ring is not formed1、R2Or R3Is any one of hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C5-C60 heterocyclic group, substituted or unsubstituted C10-C60 condensed ring group and substituted or unsubstituted C5-C60 spiro ring group.
3. The organic phosphorus luminescent material as claimed in claim 1, wherein R is1、R2、R3、R4、R5And R6All of which are hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C5-C30 heterocyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 alkylAny one of the condensed ring groups;
x is O.
4. The organic phosphorus luminescent material of claim 1, wherein the organic phosphorus luminescent material has a structural formula of any one of I-1 to I-70:
5. a method for preparing the organophosphorus luminescent material according to any one of claims 1 to 4, comprising the steps of:
1) weighing a compound (II) and iridium trichloride under a nitrogen protection system, putting the compound (II) and iridium trichloride into a reaction system, adding a solvent 1, reacting under the nitrogen protection system, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and sequentially washing and drying the precipitate with water, absolute ethyl alcohol and petroleum ether to obtain a compound (IV);
2) weighing the compound (IV) obtained in the step 1), adding alkali, adding a solvent 2 into the system, replacing nitrogen for three times, adding the compound (III) under the protection of nitrogen for reaction, cooling, carrying out suction filtration, washing with alcohol, drying, adding dichloromethane, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to finally obtain the organophosphorus luminescent material;
the structural formulas of the compound (II), the compound (III) and the compound (IV) are respectively as follows:
6. the method for preparing an organophosphorus luminescent material according to claim 5, wherein in the step 1), the molar ratio of the compound (II) to iridium trichloride is (2.2-2.5): 1.
7. The method for preparing an organophosphorus luminescent material according to claim 5, wherein in the step 1), the solvent 1 is a mixed solution of ethylene glycol ether and ultrapure water, the volume ratio of the ethylene glycol ether to the ultrapure water is 3:1, and the amount of the solvent 1 is 15 to 30 times of the mass of the iridium trichloride.
8. The method for preparing an organophosphorus light-emitting material according to claim 5, wherein the reaction time in the step 1) is 24 to 30 hours.
9. The method for preparing an organophosphorus light-emitting material according to claim 5, wherein in the step 2), the molar ratio of the compound (IV) to the compound (III) is 1 (2.5-8), the base is anhydrous potassium carbonate or anhydrous sodium carbonate, the amount of the base is 8-15 times of the mass of the compound (IV), the solvent 2 is ethylene glycol ethyl ether, the amount of the solvent 2 is 10-30 times of the mass of the compound (IV), the reaction time is 10-30 hours, and the amount of dichloromethane is 10-100 times of the mass of the compound (IV).
10. Use of an organophosphorus light-emitting material according to any one of claims 1 to 4 for the preparation of an organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911090336.0A CN110790797A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911090336.0A CN110790797A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110790797A true CN110790797A (en) | 2020-02-14 |
Family
ID=69443795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911090336.0A Withdrawn CN110790797A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790797A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102021110753A1 (en) | 2020-04-30 | 2021-11-04 | Beijing Summer Sprout Technology Co., Ltd. | Light emitting material with a polycyclic ligand |
| EP3988556A1 (en) * | 2020-10-23 | 2022-04-27 | LG Display Co., Ltd. | Organic metal compound, organic light emitting diode and organic light emitting device having the compound |
| CN114437134A (en) * | 2020-04-30 | 2022-05-06 | 北京夏禾科技有限公司 | Luminescent material with polycyclic ligand |
| CN115260243A (en) * | 2021-04-30 | 2022-11-01 | 北京夏禾科技有限公司 | Luminescent material with polycyclic ligand |
| EP4164365A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164363A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164364A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164366A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4174078A1 (en) * | 2021-10-29 | 2023-05-03 | Beijing Summer Sprout Technology Co., Ltd. | Electroluminescent material and device thereof |
-
2019
- 2019-11-08 CN CN201911090336.0A patent/CN110790797A/en not_active Withdrawn
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7278631B2 (en) | 2020-04-30 | 2023-05-22 | 北京夏禾科技有限公司 | Emissive materials with polycyclic ligands |
| DE102021110753B4 (en) | 2020-04-30 | 2023-07-13 | Beijing Summer Sprout Technology Co., Ltd. | Light-emitting material with a polycyclic ligand |
| KR102652631B1 (en) * | 2020-04-30 | 2024-04-01 | 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 | Light-emitting material with a polycyclic ligand |
| KR20210134517A (en) * | 2020-04-30 | 2021-11-10 | 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 | Light-emitting material with a polycyclic ligand |
| DE102021110753A1 (en) | 2020-04-30 | 2021-11-04 | Beijing Summer Sprout Technology Co., Ltd. | Light emitting material with a polycyclic ligand |
| CN114437134A (en) * | 2020-04-30 | 2022-05-06 | 北京夏禾科技有限公司 | Luminescent material with polycyclic ligand |
| JP2021176839A (en) * | 2020-04-30 | 2021-11-11 | 北京夏禾科技有限公司 | Light-emitting material having polycyclic ligand |
| CN114478643A (en) * | 2020-10-23 | 2022-05-13 | 乐金显示有限公司 | Organometallic compound, organic light emitting diode and organic light emitting device having the same |
| EP3988556A1 (en) * | 2020-10-23 | 2022-04-27 | LG Display Co., Ltd. | Organic metal compound, organic light emitting diode and organic light emitting device having the compound |
| TWI837528B (en) * | 2020-10-23 | 2024-04-01 | 南韓商樂金顯示科技股份有限公司 | Organic metal compound, and organic light emitting device having the compound |
| CN115260243A (en) * | 2021-04-30 | 2022-11-01 | 北京夏禾科技有限公司 | Luminescent material with polycyclic ligand |
| EP4164366A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164365A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164364A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4164363A1 (en) * | 2021-10-07 | 2023-04-12 | LG Display Co., Ltd. | Organic light emitting diode and organic light emitting device including the same |
| EP4174078A1 (en) * | 2021-10-29 | 2023-05-03 | Beijing Summer Sprout Technology Co., Ltd. | Electroluminescent material and device thereof |
| JP7464303B2 (en) | 2021-10-29 | 2024-04-09 | 北京夏禾科技有限公司 | Electroluminescent material and device thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110790797A (en) | Organic phosphorus luminescent material and preparation method and application thereof | |
| CN101460434B (en) | Materials for organic electroluminescent devices | |
| CN110698518A (en) | Organic phosphorus luminescent material and preparation method thereof | |
| JP5318812B2 (en) | Mixtures of organic light emitting semiconductors and matrix materials, their use and electronic components comprising said materials. | |
| CN101490207B (en) | Novel materials for organic electroluminescent devices | |
| CN101665521A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| JP2009170883A (en) | Organometallic compound for electro-luminescence, and organic electro-luminescent element using the same | |
| CN111423440A (en) | Red phosphorescent host compound and organic light-emitting device using same | |
| CN111808147B (en) | Organic phosphorescent material, preparation method thereof and electroluminescent device | |
| CN111187263A (en) | Phosphorescent compound, preparation method thereof and organic electroluminescent device | |
| CN110684052A (en) | Organic metal iridium complex, preparation method thereof and electroluminescent device | |
| CN110615816B (en) | Phosphorescent material, preparation method thereof and organic electroluminescent device containing phosphorescent material | |
| CN110698517B (en) | Iridium metal complex, preparation method thereof and organic electroluminescent device | |
| CN112707936A (en) | Organic light-emitting compound, preparation method thereof and organic electroluminescent device | |
| CN111205289A (en) | Phosphorescent material, preparation method thereof and organic electroluminescent device | |
| CN110760305A (en) | Phosphorescent compound, preparation method thereof and organic electroluminescent device comprising phosphorescent compound | |
| CN111377976A (en) | Organic phosphorus luminescent material and preparation method and application thereof | |
| CN112062764A (en) | Phosphorescent compound, preparation method thereof and organic electroluminescent device | |
| CN113248519A (en) | Organic compound and organic light-emitting device using same | |
| CN111471451A (en) | Organic light-emitting compound, preparation method thereof and organic electroluminescent device | |
| CN111471450A (en) | Organic light-emitting compound, preparation method thereof and organic electroluminescent device | |
| CN110862417A (en) | Phosphorescent iridium complex, preparation method thereof and electroluminescent device | |
| CN110790795B (en) | Organic phosphorus luminescent material, preparation method and application thereof | |
| CN110981915B (en) | Iridium metal complex, and preparation method and application thereof | |
| CN116332828A (en) | Dibenzocycloheptanone derivatives and application thereof in OLED (organic light emitting diode) device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200214 |