CN110698518A - Organic phosphorus luminescent material and preparation method thereof - Google Patents
Organic phosphorus luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN110698518A CN110698518A CN201911089158.XA CN201911089158A CN110698518A CN 110698518 A CN110698518 A CN 110698518A CN 201911089158 A CN201911089158 A CN 201911089158A CN 110698518 A CN110698518 A CN 110698518A
- Authority
- CN
- China
- Prior art keywords
- group
- substituted
- unsubstituted
- formula
- luminescent material
- 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- Withdrawn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 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011574 phosphorus Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 7
- 125000004431 deuterium atom Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- -1 phosphoryl group Chemical group 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000003277 amino 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims description 2
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims description 2
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 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
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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 and a preparation method thereof, wherein the organic phosphorus luminescent material has a structural general formula as follows:
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to an organophosphorus luminescent material of a nitrogen atom-containing metal iridium complex with a heterocyclic structure, and a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of being thin and light, actively emitting light, wide viewing angles, fast response, low energy consumption, excellent low temperature and shock resistance, and potentially flexible designs. In addition, the OLED can be used as a plane backlight source and an illumination light source in the display field. It is the most competitive technology in the third generation flat panel reality due to its potentially superior performance in the display technology field. Therefore, OLEDs have a promising development prospect, and further improvements in terms of lifetime and production costs are currently needed.
And the light emitting material of the organic light emitting diode is mainly a phosphorescent light emitting material. The independent light emission of three primary colors of red, blue and green is the most adopted color mode at present, and the technical key point is to improve the color purity and efficiency of the luminescent material.
As the light emitting material, excitons are formed by recombination of electrons and holes injected from each electrode. Singlet excitons emit fluorescence and triplet excitons emit phosphorescence. The singlet excitons emitted have a formation probability of 25%, while the triplet excitons emitting phosphorescence have a formation probability of 75%. Thus, triplet excitons provide greater luminous efficiency than singlet excitons. In such a phosphorescent material, the red phosphorescent material may have greater luminous efficiency than the fluorescent material. Therefore, as an important factor for improving the efficiency of the organic electroluminescent device, 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 a material with high luminous efficiency and good thermal stability is a technical problem to be solved at present.
Therefore, in combination with the above problems, it is an urgent need to solve the problems of the art to provide an organic phosphorus luminescent material and a method for preparing the same.
Disclosure of Invention
In view of the above, the present invention provides an organic phosphorus luminescent material and a preparation method thereof, and the organic phosphorus luminescent material prepared by the present invention can improve the luminous efficiency of an organic electroluminescent device as an organic luminescent material of the organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic phosphorus luminescent material, the molecular structure general formula of which is:
in the formula I, R1, R2, R3, R4, R5, R6 and R7 are selected from a hydrogen atom, a deuterium atom, halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, a sulfonic group, a sulfonyl group, a phosphoryl group, a substituted or unsubstituted alkyl group of C1-C60, a substituted or unsubstituted aryl group of C6-C60, a substituted or unsubstituted cycloalkyl group of C3-C30, a substituted or unsubstituted alkoxy group of C1-C60, a substituted or unsubstituted alkylamino group of C1-C60, a substituted or unsubstituted alkenyl group of C2-C60, a substituted or unsubstituted alkynyl group of C2-C60, a substituted or unsubstituted heterocyclic group of C5-C60, a substituted or unsubstituted condensed ring group of C10-C60, and a substituted or unsubstituted spirocyclic group of C5-C60;
x in the formula I is N or P;
in the formula I, R1, R2 and R3 represent any positions of a ring, R1 and R3 represent single, two, three or no substituents, R2 and R6 represent single, two or no substituents, and R4, R5 and R7 represent single or no substituents;
the atoms of the above groups or substituents may be deuterated.
Preferably, R1, R2, R3 and R4 form a condensed ring or an aromatic heterocyclic ring with each other independently from other substituents on the ring, and the substituents which do not form the condensed ring or the aromatic heterocyclic ring are selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C5-C60 heterocyclic group, a substituted or unsubstituted C10-C60 condensed ring group and a substituted or unsubstituted C5-C60 spiro ring group.
Preferably, the R1, R2, R3, R4, R5, R6 and R7 are selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C5-C30 heterocyclic group, a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C10-C30 condensed ring group.
Preferably, X is N.
Preferably, the organic phosphorus luminescent material has a structural formula of any one of I-1 to I-94:
preferably, the formulas I-1 to I-94 list some specific structural forms, but the series of compounds is not limited to these molecular structures.
A preparation method of an organic phosphorus luminescent material comprises the following steps:
s1, weighing a compound represented by the following structural formula (II) under a nitrogen protection system, respectively adding the compound and iridium trichloride into a solvent for reaction for 24-30h, refluxing under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, respectively washing the precipitate with water, absolute ethyl alcohol and petroleum ether, and drying to obtain a compound represented by the formula (IV);
s2, weighing the compound of the formula (IV) obtained in the step S1, and adding anhydrous potassium carbonate, wherein the mass ratio of the anhydrous potassium carbonate to the compound of the formula (IV) is 8-15: adding ethylene glycol ethyl ether, wherein the mass ratio of the ethylene glycol ethyl ether to the compound of the formula (IV) is 10-30: 1, replacing nitrogen for three times with reaction time of 10-30h, adding a compound of a formula (III) under the protection of nitrogen, refluxing for 24h under the protection of nitrogen, cooling to room temperature, performing suction filtration, washing with alcohol, drying, taking dichloromethane as a solvent, wherein the mass ratio of the dichloromethane to the compound of the formula (IV) is 10-100: 1, carrying out neutral alumina column chromatography, concentrating the filtrate, and precipitating a solid to obtain the organophosphorus luminescent material shown in the formula (I).
Preferably, the groups R1, R2, R3 and R4 in the compound of formula (IV) in step S1 are the same as the groups R1, R2, R3 and R4 in the compound of formula (II).
Preferably, the molar ratio of the compound of formula (II) in the step S1 to iridium trichloride is 2.2-2.5: 1.
Preferably, the solvent in step S1 is a mixed solution of ethylene glycol ethyl ether and ultrapure water.
Preferably, the volume ratio of the ethylene glycol ethyl ether to the ultrapure water in the step S1 is 3: 1.
preferably, the mass ratio of the solvent to the iridium trichloride in the step S1 is 15-30: 1.
preferably, the R5, R6 and R7 groups of the compound of formula (I) in step S2 are the same as the R5, R6 and R7 groups of the compound of formula (III).
Preferably, the molar ratio of the compound of formula (IV) to the compound of formula (III) in step S2 is 1: 2.5-8.
Preferably, the anhydrous potassium carbonate in step S2 may be replaced with anhydrous sodium carbonate.
Preferably, in the step S2, the reaction time is 10-30h, preferably 20-24 h.
An organic phosphor luminescent material is applied to the preparation of organic electroluminescent devices.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the raw materials are easy to obtain, and the preparation method is simple.
2. The organic phosphorus luminescent material prepared by the invention can be used as an organic luminescent material of an organic electroluminescent device to improve the luminous efficiency and the service life of the device.
Detailed Description
The technical solutions in the embodiments of the present invention are 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 embodiment 1 of the invention discloses an organic phosphorus luminescent material and a preparation method thereof, and the adopted technical scheme is as follows:
the preparation method is characterized in that the compound of the formula I-1,
weighing IrC1 mmol of formula II-124 under the protection of nitrogen3·3H2010mmo1 is put into a reaction system, a mixed solution of 180m1 ethylene glycol ethyl ether and 60m1 purified water is added, the mixture is refluxed for 25 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand IV-1 obtained was 6.10g as a dark red powder, with a yield of 76%.
Then weighing the bridged 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. Using dichloromethane as solvent, using neutral alumina column chromatography, concentrating the filtrate and precipitating solid to obtain red organic phosphorus luminescent material shown in formula I-1, the mass is 3.43 g. The yield was 70% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 979.32; the test value was 979.65.
Elemental analysis calculated as C65.00; h is 6.38; 19.63 parts of Ir; n is 5.72; o is 3.27; test value C: 65.01; h is 6.39; 19.63 parts of Ir; n is 5.71; o is 3.26.
Example 2
The embodiment 2 of the invention discloses an organic phosphorus luminescent material and a preparation method thereof, and the adopted technical scheme is as follows:
the preparation method is characterized in that the compound of the formula I-53,
weighing IrC1 mmol of formula II-5325 under nitrogen protection3·3H2010mmo1 is put into a reaction system, a mixed solution of 210m1 ethylene glycol ethyl ether and 70m1 purified water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand IV-53 obtained was 6.26g as a dark red powder, with a yield of 73%.
Adding anhydrous potassium carbonate into the bridged ligand IV-533 mmol, adding 60ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12mmol under nitrogen, refluxing for 24 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organophosphorus luminescent material shown in the formula I-53, wherein the mass of the red organophosphorus luminescent material is 4.65g, the yield of the red organophosphorus luminescent material is 75%, and the HPLC purity is more than 99.5%.
Mass spectrum calculated 1035.43 test 1035.59.
Elemental analysis, calculated value is C66.12; h is 6.81; 18.56 parts of Ir; n is 5.41; o is 3.09. The test value is C: 66.11; h is 6.80; 18.57 parts of Ir; n is 5.42; o is 3.08.
Example 3
The embodiment 3 of the invention discloses an organic phosphorus luminescent material and a preparation method thereof, and the adopted technical scheme is as follows:
the preparation method is characterized in that the compound is shown in the formula I-83,
weighing IrC 1-8325 mmol of ligand II under the protection of nitrogen3·3H2010mmo1 is put into a reaction system, mixed solution of 210m1 ethylene glycol ethyl ether and 70m1 purified water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing, drying and drying in sequence. The mass of the bridged ligand IV-83 obtained was 5.8g as a dark red powder, with a yield of 63%.
Adding anhydrous potassium carbonate into the bridged ligand IV-533 mmol, adding 60ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding 3, 7-diethyl-4, 6-nonanedione 12mmol under nitrogen, refluxing for 24 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organophosphorus luminescent material shown in the formula I-53, wherein the mass of the red organophosphorus luminescent material is 4.3g, the yield of the red organophosphorus luminescent material is 65%, and the HPLC purity is more than 99.5%.
Mass spectrum calculated 1103.48 test 1103.42.
Elemental analysis calculated as C68.57; h is 6.03; 17.42 parts of Ir; n is 5.08; o is 2.90, and the test value is C is 68.58; h is 6.04; 17.41 parts of Ir; n is 5.06; o is 2.91.
Example 4
The embodiment 4 of the invention discloses an organic phosphorus luminescent material and a preparation method thereof, and the adopted technical scheme is as follows:
the preparation method is characterized in that the compound is shown in the formula I-88,
weighing IrC1 mmol of formula II-8822 under the protection of nitrogen3·3H2010mmo1 is put into a reaction system, a mixed solution of 120m1 ethylene glycol ethyl ether and 40m1 purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand IV-88 obtained was 6.03g as a dark red powder, with a yield of 78%.
Then weighing the bridged ligand IV-882.5 mmol, adding anhydrous potassium carbonate 25mmol, adding 30ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 2, 8-dimethyl-3, 7-diisopropyl-4, 6-nonanedione 12.5mmol under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in the formula I-88, wherein the mass of the red organic phosphorus luminescent material is 3.27 g. The yield was 65% with an HPLC purity of greater than 99.5%.
Mass spectrum: calculated value 1007.48; the test value was 1007.32.
Elemental analysis: the calculated value is C65.58; h is 6.60; 19.08 parts of Ir; n is 5.56; o is 3.18. Test value C65.59; h is 6.61; 19.07 parts of Ir; n is 5.58; o is 3.17.
Example 5
The embodiment 5 of the invention discloses an organic phosphorus luminescent material and a preparation method thereof, and the adopted technical scheme is as follows:
the preparation method is shown in the formula I-94,
weighing IrC1 mmol of formula II-9425 under the protection of nitrogen3·3H2010mmo1 is put into a reaction system, mixed solution of 225m1 ethylene glycol ethyl ether and 75m1 purified water is added, the mixture is refluxed for 28 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand IV-94 was obtained as a dark red powder in a mass of 4.63g with a yield of 70%.
Then weighing the bridged ligand IV-943 mmol, adding 30mmol of anhydrous potassium carbonate, adding 90ml of ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding 18mmol of 2, 8-dimethyl-3, 7-diisopropyl-4, 6-nonanedione under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the red organic phosphorus luminescent material shown in the formula I-94, wherein the mass of the red organic phosphorus luminescent material is 4.18 g. The yield was 78% and the HPLC purity was greater than 99.5%.
Mass spectrum: calculated 895.16 with test value 895.36.
Elemental analysis: calculated value is C: 63.06; h is 5.63; 21.47 parts of Ir; n is 6.26; o is 3.57. Test value C is 63.08; h is 5.65; 21.46 parts of Ir; n is 6.25; o is 3.55.
The synthesis methods of other compounds are the same as those described above, and further description is omitted, and the mass spectrum or molecular formula of other synthesis examples is shown in the following table:
example 6
The present invention is provided to further prove the beneficial effects of the prepared organic phosphorus luminescent material. The invention also provides an organic electroluminescent device which is made of the organic phosphorus luminescent material prepared by the technical scheme of the invention, and more particularly made of the organic phosphorus luminescent material shown in the formula I.
Organic electroluminescent devices are prepared using organic phosphorus luminescent materials of formula i-1, which are 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. Under vacuum conditions, the standard pressure was set at 1X 10-6 Torr. Thereafter on an ITO substrateCBP + type
And
the sequence of (a) and (b) forming layers of organic material.
The organic electroluminescent device prepared as described above was applied with a forward direct current bias voltage, the organic electroluminescent characteristics were measured using a PR-650 photometry instrument of Photo Research, and the lifetime of T95 was measured using a lifetime measuring apparatus of McScience. The results are shown in Table 1.
TABLE 1
As shown in the table, the compound of the present invention has a lower voltage and a significantly improved current efficiency under the same current. By using the compound obtained by the present invention as a light emitting layer of an organic electroluminescent device, the present invention provides an organic electroluminescent device having excellent color purity and brightness and prolonged durability.
Comparative example 1
An organic electroluminescent device was fabricated in the same manner as in example 6, except that the red light-doping compound of the light-emitting layer was (btp)2Ir (acac). Wherein the compounds used in embodiments of the present invention are copper (II) phthalocyanine (CuPc), NPB, (btp)2Ir (acac), Alq3And structural formula of CBP.
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 embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
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. Accordingly, the invention is not 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 (9)
1. An organic phosphorus luminescent material is characterized in that the molecular structure general formula is as follows:
in the formula I, R1, R2, R3, R4, R5, R6 and R7 are selected from a hydrogen atom, a deuterium atom, halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, a sulfonic group, a sulfonyl group, a phosphoryl group, a substituted or unsubstituted alkyl group of C1-C60, a substituted or unsubstituted aryl group of C6-C60, a substituted or unsubstituted cycloalkyl group of C3-C30, a substituted or unsubstituted alkoxy group of C1-C60, a substituted or unsubstituted alkylamino group of C1-C60, a substituted or unsubstituted alkenyl group of C2-C60, a substituted or unsubstituted alkynyl group of C2-C60, a substituted or unsubstituted heterocyclic group of C5-C60, a substituted or unsubstituted condensed ring group of C10-C60, and a substituted or unsubstituted spirocyclic group of C5-C60;
x in the formula I is N or P;
the atoms of the above groups or substituents may be deuterated.
2. An organophosphorus light emitting material according to claim 1, wherein each of R1, R2, R3 and R4 is independently fused ring or aromatic heterocyclic ring with the ring, and the substituent not fused ring or aromatic heterocyclic ring is selected from hydrogen atom, deuterium atom, substituted or unsubstituted C1-C60 alkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C3-C60 cycloalkyl group, substituted or unsubstituted C5-C60 heterocyclic group, substituted or unsubstituted C10-C60 fused ring group, and substituted or unsubstituted C5-C60 spiro ring group.
3. An organophosphorus light emitting material according to claim 1, wherein said R1, R2, R3, R4, R5, R6 and R7 are all selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C5-C30 heterocyclic group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C10-C30 condensed ring group.
4. The organic phosphorus luminescent material as claimed in claim 1, wherein the organic phosphorus luminescent material has a structural formula of any one of I-1 to I-94:
5. a method for preparing the organophosphorus luminescent material described in any one of claims 1 to 4, comprising the steps of:
s1, weighing a compound represented by the following structural formula (II) under a nitrogen protection system, respectively adding the compound and iridium trichloride into a solvent for reaction for 24-30h, refluxing under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, respectively washing the precipitate with water, absolute ethyl alcohol and petroleum ether, and drying to obtain a compound represented by the formula (IV);
s2, weighing the compound of the formula (IV) obtained in the step S1, and adding anhydrous potassium carbonate, wherein the mass ratio of the anhydrous potassium carbonate to the compound of the formula (IV) is 8-15: adding ethylene glycol ethyl ether, wherein the mass ratio of the ethylene glycol ethyl ether to the compound of the formula (IV) is 10-30: 1, replacing nitrogen for three times with reaction time of 10-30h, adding a compound of a formula (III) under the protection of nitrogen, refluxing for 24h under the protection of nitrogen, cooling to room temperature, performing suction filtration, washing with alcohol, drying, taking dichloromethane as a solvent, wherein the mass ratio of the dichloromethane to the compound of the formula (IV) is 10-100: 1, carrying out neutral alumina column chromatography, concentrating the filtrate, and precipitating a solid to obtain the organophosphorus luminescent material shown in the formula (I).
6. The method for preparing an organophosphorus luminescent material according to claim 5, wherein the molar ratio of the compound of formula (II) in step S1 to iridium trichloride is 2.2-2.5: 1.
7. The method according to claim 5, wherein the solvent in step S1 is a mixed solution of ethylene glycol ethyl ether and ultrapure water, the volume ratio of ethylene glycol ethyl ether to ultrapure water is 3:1, and the mass ratio of the solvent to iridium trichloride is 15-30: 1.
8. the method of claim 5, wherein in step S2, the molar ratio of the compound of formula (IV) to the compound of formula (III) is 1: 2.5-8.
9. Use of an organophosphorus light-emitting material according to any one of claims 1 to 5 for the preparation of an organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911089158.XA CN110698518A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911089158.XA CN110698518A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110698518A true CN110698518A (en) | 2020-01-17 |
Family
ID=69204738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911089158.XA Withdrawn CN110698518A (en) | 2019-11-08 | 2019-11-08 | Organic phosphorus luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110698518A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR20210134517A (en) * | 2020-04-30 | 2021-11-10 | 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 | 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 |
| CN115215907A (en) * | 2021-04-16 | 2022-10-21 | 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 |
| EP4174078A1 (en) * | 2021-10-29 | 2023-05-03 | Beijing Summer Sprout Technology Co., Ltd. | Electroluminescent material and device thereof |
| JP2023068659A (en) * | 2021-11-02 | 2023-05-17 | 北京夏禾科技有限公司 | Electroluminescent material and device |
-
2019
- 2019-11-08 CN CN201911089158.XA patent/CN110698518A/en not_active Withdrawn
Cited By (15)
| 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 |
| KR20210134517A (en) * | 2020-04-30 | 2021-11-10 | 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 | Light-emitting material with a 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 |
| CN114437134A (en) * | 2020-04-30 | 2022-05-06 | 北京夏禾科技有限公司 | Luminescent material with polycyclic ligand |
| KR102652631B1 (en) * | 2020-04-30 | 2024-04-01 | 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 | Light-emitting material with a polycyclic ligand |
| DE102021110753B4 (en) | 2020-04-30 | 2023-07-13 | Beijing Summer Sprout Technology Co., Ltd. | Light-emitting material with a polycyclic ligand |
| 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 |
| 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 |
| 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 |
| CN115215907A (en) * | 2021-04-16 | 2022-10-21 | 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 |
| 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 |
| JP2023068659A (en) * | 2021-11-02 | 2023-05-17 | 北京夏禾科技有限公司 | Electroluminescent material and device |
| JP7511922B2 (en) | 2021-11-02 | 2024-07-08 | 北京夏禾科技有限公司 | Electroluminescent materials and devices thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110698518A (en) | Organic phosphorus luminescent material and preparation method thereof | |
| CN110790797A (en) | Organic phosphorus luminescent material and preparation method and application thereof | |
| KR101105619B1 (en) | Mixtures of organic emissive semiconductors and matrix materials, their use and electronic components comprising said materials | |
| KR20090058063A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| CN101490207A (en) | Novel materials for organic electroluminescent devices | |
| KR20090093688A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20170039020A (en) | Organic electroluminescent compound and organic electroluminescent device | |
| CN113004340B (en) | Metal complex, organic electroluminescent material and organic electroluminescent element comprising same | |
| CN110128403B (en) | Compound, display panel and display device | |
| CN111747932B (en) | Compound, application thereof and organic electroluminescent device | |
| CN111423440A (en) | Red phosphorescent host compound and organic light-emitting device using same | |
| CN101209988B (en) | Phenanthrene series derivatives and organic light-emitting diode containing the same | |
| CN110684052A (en) | Organic metal iridium complex, preparation method thereof and electroluminescent device | |
| CN111333684A (en) | Organic iridium metal complex and preparation method and application thereof | |
| CN110669077A (en) | Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device | |
| 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 | |
| CN111484839A (en) | Organic light-emitting compound, preparation method thereof and organic electroluminescent device | |
| CN110615816A (en) | Phosphorescent material, preparation method thereof and organic electroluminescent device containing phosphorescent material | |
| CN110862290A (en) | Compound containing anthrene structure and application thereof in organic electroluminescent device | |
| CN111377976A (en) | Organic phosphorus luminescent material and preparation method and application thereof | |
| CN114716467A (en) | Heterocyclic compound containing boron and nitrogen and application thereof in organic electroluminescent device | |
| JP2023553973A (en) | Binuclear metal platinum complexes and their applications | |
| CN111471450A (en) | Organic light-emitting compound, preparation method thereof and organic electroluminescent device | |
| CN112062764A (en) | Phosphorescent compound, preparation method thereof and organic electroluminescent 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 |
Application publication date: 20200117 |
|
| WW01 | Invention patent application withdrawn after publication |