CN104628638A - Blue-ray organic electroluminescent material, as well as preparation method and organic electroluminescent device thereof - Google Patents
Blue-ray organic electroluminescent material, as well as preparation method and organic electroluminescent device thereof Download PDFInfo
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- CN104628638A CN104628638A CN201310567499.XA CN201310567499A CN104628638A CN 104628638 A CN104628638 A CN 104628638A CN 201310567499 A CN201310567499 A CN 201310567499A CN 104628638 A CN104628638 A CN 104628638A
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 241001025261 Neoraja caerulea Species 0.000 title abstract 3
- 238000001035 drying Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- -1 tris-argon benzyl acetone Chemical compound 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229940126062 Compound A Drugs 0.000 claims description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 4
- BWFOVZDGMFZPFX-UHFFFAOYSA-N 9,10-dibromo-2-tert-butylanthracene Chemical compound C1=CC=CC2=C(Br)C3=CC(C(C)(C)C)=CC=C3C(Br)=C21 BWFOVZDGMFZPFX-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZDWQXFNUOPAKSC-UHFFFAOYSA-N OBO.N1=CC=CC2=CC=CC=C21 Chemical compound OBO.N1=CC=CC2=CC=CC=C21 ZDWQXFNUOPAKSC-UHFFFAOYSA-N 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of organic electroluminescent materials, and discloses a blue-ray organic electroluminescent material, as well as a preparation method and an organic electroluminescent device thereof. The material has a structural formula as shown in the specification. In the blue-ray organic electroluminescent material, quinoline is a relatively good electron transmission unit and has good thermal stability; and anthracene has relatively high fluorescence quantum yield, and the luminescence efficiency of the organic electroluminescent device can be improved by using the material as a luminescent layer material.
Description
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a blue light organic electroluminescent material and a preparation method thereof. The invention also relates to an organic electroluminescent device adopting the blue light organic electroluminescent material as a main material of a luminescent layer.
Background
Organic electroluminescence has features of low voltage dc driving, high brightness, wide visibility, etc., and is considered to be one of the most promising next-generation flat panel display technologies (c.w.tang and s.a.vanslyke.appl.phys.lett.,1987,51(12): 913-915). The organic molecule electroluminescent device is mostly composed of more than two layers of organic molecule films, and the organic molecule films respectively have electron and hole transmission performance. The organic polymer electroluminescent device only needs a single organic film (J.H. Burroughes, D.D.C. Bradley, A.R.Brown, R.N. marks, K.Mackay, R.H. friend, P.L.Burns and A.B.Holms. Nature,1990,347: 539) 541), so that the preparation process is more convenient. The reduction of the interface of the molecular layer device is beneficial to the stability of the device. Organic molecular electroluminescent devices require more than two thin films because they are dominated by either transporting electrons or transporting holes due to the limitations of the carrier transport properties of the organic molecules used. The performance of organic molecules depends on the structure, the carrier transmission characteristic of the organic molecules is related to a conjugated system of the molecules, a polyaromatic conjugated system often has electron transmission performance, and triarylamine molecules have hole transmission performance, so that various organic light-emitting molecular materials with different performances can be obtained through molecular design at present, but the organic light-emitting molecular materials have the defects of high price, complex preparation and glass transition temperature (T)g) Low, low carrier transport performance, and the like.
Disclosure of Invention
The invention aims to provide a blue light organic electroluminescent material with higher glass transition temperature and carrier transmission performance.
In order to achieve the purpose, the structure of the blue light organic electroluminescent material provided by the invention is as follows:
namely 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline).
Another object of the present invention is to provide a method for preparing a blue organic electroluminescent material with simple synthetic route, low cost and easy availability, the method comprising the following steps:
compounds A and B are provided, respectively, represented by the following structural formulae,
adding a compound A and a compound B into an organic solvent containing a catalyst and an alkali solution in an oxygen-free environment for dissolving, wherein the molar ratio of the compound A to the compound B is 1: 2-2.4, carrying out Suzuki coupling reaction on a mixed solution obtained after dissolving at 70-130 ℃ for 12-48 hours, stopping the reaction, cooling to room temperature, and separating and purifying the reaction solution to obtain the blue light organic electroluminescent material with the following structural formula:
wherein the catalyst is bis-triphenylphosphine palladium dichloride or tetrakis triphenylphosphine palladium; or,
the catalyst is a mixture of organic palladium and an organic phosphine ligand, and the molar ratio of the organic palladium to the organic phosphine ligand is 1: 4-8; preferably, the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium, and the organic phosphine ligand is tris (o-methylphenyl) phosphine or 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl; more preferably, the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon benzylacetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
The molar ratio of the catalyst to the compound A is 1: 20-1: 100.
In the preparation method, the alkali solution is at least one selected from a sodium carbonate solution, a potassium carbonate solution and a sodium bicarbonate solution; in the alkaline solution, the molar ratio of the alkaline solute to the compound A is 20: 1.
In a preferred embodiment, the organic solvent is selected from at least one of toluene, N-dimethylformamide, tetrahydrofuran.
In a preferred embodiment, the reaction temperature of the Suzuki coupling reaction is 90-120 ℃, and the reaction time is 24-36 hours.
In a preferred embodiment, the separation and purification reaction liquid includes:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material.
In the preparation method, the oxygen-free environment is composed of at least one gas of argon and nitrogen.
The preparation method has the advantages of simple principle, simple and convenient operation, low requirement on equipment and wide popularization and application.
The invention also aims to provide application of the blue light organic electroluminescent material in a light-emitting layer of an organic electroluminescent device.
The organic electroluminescent device structurally comprises a conductive substrate, a hole injection layer, a hole transmission/electron blocking layer, a light emitting layer, an electron transmission/hole blocking layer, an electron injection layer and a cathode layer, wherein the hole injection layer, the hole transmission/electron blocking layer, the light emitting layer, the electron transmission/hole blocking layer, the electron injection layer and the cathode layer are sequentially stacked on the surface of the conductive substrate; wherein:
the conductive substrate comprises a glass substrate and an anode layer deposited on the surface of the glass substrate, wherein the anode layer is made of Indium Tin Oxide (ITO);
the hole injection layer is made of PEDOT (PSS);
the hole transport/electron blocking layer is made of N, N '-diphenyl-N, N' -di (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD);
the material of the luminescent layer is the blue light organic electroluminescent material, namely 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline);
the material of the electron transport/hole blocking layer is 4, 7-diphenyl-1, 10-phenanthroline (BPhen);
the electron injection layer is made of LiF;
the cathode layer is made of Al.
In the blue light organic electroluminescent material provided by the invention, quinoline is a better electron transmission unit and has good thermal stability; the anthracene has higher fluorescence quantum yield, and the material is used as a luminescent layer material, so that the luminescent efficiency of the organic electroluminescent device can be improved.
The preparation method of the blue light organic electroluminescent material adopts a simpler synthetic route, thereby reducing the process flow, and the raw materials are cheap and easy to obtain, so that the manufacturing cost is reduced.
Drawings
FIG. 1 is a thermogravimetric analysis chart of a blue organic electroluminescent material prepared in example 1;
fig. 2 is a schematic view of the structure of an organic electroluminescent device prepared in example 5.
Detailed Description
For better understanding of the contents of the present patent, the technical scheme of the present invention is further illustrated below by specific examples and illustrations, including material preparation and device preparation, but the present invention is not limited by these examples, wherein compound a and compound B are both available from carbofuran technology.
Example 1: the blue-light organic electroluminescent material of the embodiment, namely 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline), is prepared by the following steps:
under the protection of argon, 9, 10-dibromo-2-tert-butylanthracene (78mg,0.2mmol) and 2, 4-diphenyl-6-pinacol boronic acid ester quinoline (163mg,0.4mmol) are added into a flask containing 10mL of a toluene solvent, after full dissolution, a potassium carbonate (2mL,2mol/L) solution is added into the flask, vacuum is conducted to remove oxygen and argon is filled, and then bis-triphenylphosphine palladium dichloride (5.6 mg,0.008 mmol) is added; the flask was heated to 120 ℃ for a Suzuki coupling reaction for 24 h. Stopping the reaction, cooling to room temperature, extracting the reaction liquid for multiple times by using dichloromethane, merging an organic phase, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material. The yield was 82%. Mass spectrum: m/z793.0 (M)++ 1); elemental analysis (%) C60H44N2Theoretical value: c90.87, H5.59, N3.53; measured value: c90.79, H5.72, N3.48.
FIG. 1 shows blue light obtained in example 1Thermogravimetric analysis of organic electroluminescent material; thermogravimetric analysis was performed by a Perkin-Elmer Series7 thermoanalysis system, all measurements being performed in a room temperature atmosphere. As can be seen from FIG. 1, the thermal weight loss temperature (T) of the blue-light organic electroluminescent material is 5%d) Is 380 ℃.
Example 2: the blue-light organic electroluminescent material of the embodiment has a structure of 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline), and is prepared by the following steps:
under the protection of a mixed gas of nitrogen and argon, 9, 10-dibromo-2-tert-butylanthracene (118mg,0.3mmol), 2, 4-diphenyl-6-pinacol boronic acid ester quinoline (269mg,0.66mmol) and 15mL of tetrahydrofuran were added to a 50 mL-standard two-necked flask, and after fully dissolving, a mixed gas of nitrogen and argon was purged for about 20min, and then tetratriphenylphosphine palladium (4 mg,0.003 mmol) was added thereto, and after fully dissolving, a solution of sodium bicarbonate (3mL,2mol/L) was added. After the mixture of nitrogen and argon was fully purged for about 10min, the two bottles were charged to 70 ℃ to conduct Suzuki coupling reaction for 48 hours. Stopping the reaction, cooling to room temperature, extracting the reaction liquid for multiple times by using dichloromethane, merging an organic phase, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material. The yield was 75%.
Example 3: the blue-light organic electroluminescent material of the embodiment has a structure of 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline), and is prepared by the following steps:
under the protection of nitrogen, 9, 10-dibromo-2-tert-butylanthracene (118mg,0.3mmol), 2, 4-diphenyl-6-pinacol boronate quinoline (281mg,0.69mmol), palladium acetate (3.5mg,0.015mmol) and tris (o-methylphenyl) phosphine (21mg, 0.06mmol) were added to a flask containing 12mL of N, N-dimethylformamide, and after sufficient dissolution, a potassium carbonate (3mL,2mol/L) solution was added, followed by purging the flask with nitrogen for about 30 min; the flask was heated to 130 ℃ for a Suzuki coupling reaction for 12 h. Stopping the reaction, cooling to room temperature, extracting the reaction liquid for multiple times by using dichloromethane, merging an organic phase, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material. The yield was 83%.
Example 4: the blue-light organic electroluminescent material of the embodiment has a structure of 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline), and is prepared by the following steps:
9, 10-dibromo-2-tert-butylanthracene (118mg,0.3mmol), 2, 4-diphenyl-6-pinacol boronate quinoline (293mg,0.72mmol), tris-argon-benzylacetone dipalladium (9mg,0.009mmol) and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (29mg, 0.072mmol) were added to a flask containing 12mL of N, N-dimethylformamide under nitrogen protection, and after sufficient dissolution, a solution of sodium carbonate (3mL,2mol/L) was added. Then introducing nitrogen into the flask to exhaust air for about 30 min; the flask was heated to 90 ℃ for a Suzuki coupling reaction for 36 h. Stopping the reaction, cooling to room temperature, extracting the reaction liquid for multiple times by using dichloromethane, merging an organic phase, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material. The yield was 86%.
Example 5:
this embodiment is an organic electroluminescent device, and the material of the light emitting layer is the blue light organic electroluminescent material prepared by the present invention, i.e. 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline).
As shown in fig. 2, the organic electroluminescent device comprises a conductive substrate 1, and a hole injection layer 2, a hole transport/electron blocking layer 3, a light emitting layer 4, an electron transport/hole blocking layer 5, an electron injection layer 6, and a cathode layer 7 sequentially stacked on the surface of the conductive substrate; wherein:
the conductive substrate 1 comprises a glass substrate and an anode layer deposited on the surface of the glass substrate, wherein the anode layer is made of Indium Tin Oxide (ITO); combining ITO with glass, namely ITO glass for short;
the material of the hole injection layer 2 is PEDOT, PSS;
the hole transport/electron blocking layer 3 is made of N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD);
the material of the light-emitting layer 4 is 6, 6' - (2-tert-butylanthracene-9, 10-diyl) bis (2, 4-diphenylquinoline) (represented by P);
the material of the electron transport/hole blocking layer 5 is 4, 7-diphenyl-1, 10-phenanthroline (BPhen);
the electron injection layer 6 is made of LiF;
the cathode layer 7 is made of Al.
The specific method for manufacturing the organic electroluminescent device comprises the following steps:
firstly, spin-coating PEDOT (PSS) on an anode layer (ITO) of a cleaned conductive substrate, and drying to obtain a hole injection layer (PEDOT: PSS);
then, a hole transport/electron blocking layer (TPD), a light emitting layer (P), an electron transport/hole blocking layer (BPhen), an electron injection Layer (LiF), and a cathode layer (Al) were sequentially deposited by vapor deposition on the surface of the hole injection layer.
Therefore, the structure of the organic electroluminescent device can also be expressed as:
glass/ITO (150 nm)/PEDOT PSS (30nm)/TPD (40nm)/P (30 nm)/BPhen (35nm)/LiF (1.5nm)/Al (150 nm); wherein the diagonal bars indicate the layered structure and the numerical values in parentheses indicate the thickness values of the respective functional layers.
The organic electroluminescent device was tested for current-luminance-voltage characteristics by a Keithley source measuring system (Keithley 2400source meter) with a calibrated silicon photodiode, all in a room temperature atmosphere. The test result shows that: the starting voltage of the device is 4.5V and is 1000cd/m2The lumen efficiency is 5.2 lm/W.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A blue light organic electroluminescent material is characterized in that the structure is as follows:
2. a method for preparing the blue organic electroluminescent material according to claim 1, comprising the steps of:
compounds A and B are provided, respectively, represented by the following structural formulae,
adding a compound A and a compound B with a molar ratio of 1: 2-2.4 into an organic solvent containing a catalyst and an alkali solution in an oxygen-free environment for dissolving, carrying out Suzuki coupling reaction on the obtained mixed solution at 70-130 ℃ for 12-48 hours, stopping the reaction, cooling to room temperature, and separating and purifying the reaction solution to obtain the blue light organic electroluminescent material with the following structural formula:
3. the preparation method of the blue light organic electroluminescent material according to claim 2, wherein the catalyst is bis-triphenylphosphine palladium dichloride or tetrakis-triphenylphosphine palladium; the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
4. The preparation method of the blue-light organic electroluminescent material according to claim 2, wherein the catalyst is a mixture of organic palladium and an organic phosphine ligand, and the molar ratio of the organic palladium to the organic phosphine ligand is 1: 4-8; the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
5. The method for preparing a blue light organic electroluminescent material according to claim 4, wherein the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium, and the organic phosphine ligand is tris (o-methylphenyl) phosphine or 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
6. The method for preparing a blue light organic electroluminescent material according to claim 5, wherein the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon-benzylacetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
7. The method of claim 2, wherein the alkali solution is at least one selected from a sodium carbonate solution, a potassium carbonate solution, and a sodium bicarbonate solution; in the alkaline solution, the molar ratio of the alkaline solute to the compound A is 20: 1.
8. The method for preparing a blue organic electroluminescent material according to claim 2, wherein the organic solvent is at least one selected from the group consisting of toluene, N-dimethylformamide, and tetrahydrofuran.
9. The method for preparing a blue organic electroluminescent material according to any one of claims 2 to 8, wherein the separation and purification reaction solution comprises:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material.
10. An organic electroluminescent device, characterized in that the material of its luminescent layer is the blue light organic electroluminescent material of claim 1.
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