CN104592973A - Blue-light-emitting organic electroluminescent material, and preparation method and application thereof - Google Patents
Blue-light-emitting organic electroluminescent material, and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- -1 tris-argon benzyl acetone Chemical compound 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- 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 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000003208 petroleum Substances 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
- 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
- 150000001875 compounds Chemical class 0.000 claims description 6
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- 239000003446 ligand Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 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
- 239000000126 substance 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 13
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- 239000000758 substrate Substances 0.000 description 13
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- 229910052786 argon Inorganic materials 0.000 description 7
- 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
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 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
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- 238000002411 thermogravimetry Methods 0.000 description 3
- 0 CC(C)(C)c(ccc1c(*)c2c3cccc2)cc1c3N Chemical compound CC(C)(C)c(ccc1c(*)c2c3cccc2)cc1c3N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 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
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process 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
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
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- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a blue-light-emitting organic electroluminescent material, and a preparation method and application thereof, belonging to the field of organic electroluminescent device materials. Shown below is the structural formula of the material. In the blue-light-emitting organic electroluminescent material provided by the invention, fluorene has a large rigid plane structure and good thermal stability, and anthracene has high fluorescent quantum yield; therefore, an organic electroluminescent device based on the material facilitates improvement of luminous efficiency.
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 and application thereof.
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 better 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 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene.
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 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 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 tri-o-tolylphosphine, 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 at least one selected from the group consisting of toluene, N-dimethylformamide, and 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 with dichloromethane for multiple times, merging organic phases, drying the organic phases with 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 leacheate (the structure of which can be expressed as petroleum ether: ethyl acetate (10: 1)) with the volume ratio of 10:1 through a silica gel chromatography 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 anode 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 conductive anode substrate; wherein:
the conductive anode substrate comprises a glass substrate and a conductive anode layer deposited on the surface of the glass substrate, wherein the conductive anode layer is made of Indium Tin Oxide (ITO), so the conductive anode substrate is also called ITO glass or is directly called ITO for short;
the material used as the hole injection layer is 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 2-tert-butyl-9, 10-di (4- (9-phenyl-9H-fluorene-9-yl) phenyl) anthracene;
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, fluorene has a large rigid planar structure and good thermal stability; anthracene has a high fluorescence quantum yield; therefore, the organic electroluminescent device based on the material is beneficial to improving the luminous efficiency.
In addition, the preparation method of the blue light organic electroluminescent material adopts a simpler synthesis route, thereby reducing the process flow, having cheap and easily obtained raw materials and reducing the manufacturing cost:
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 present example, i.e. 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene, was prepared by the following steps:
under the protection of argon, 9, 10-dibromo-2-tert-butylanthracene (78mg,0.2mmol) and 9- (4-pinacolboronic acid ester phenyl) -9-phenyl-9H-fluorene (178mg,0.4mmol) are added into a flask containing 10mL of toluene solvent, after full dissolution, a potassium carbonate (2mL,2mol/L) solution is added into the flask, vacuum is pumped for deoxygenation 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 reaction, cooling to room temperature, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous magnesium sulfate, spin-drying, and separating the crude product with petroleum ether and ethyl acetate (10:1) as eluent by silica gel chromatography column to obtain white crystals. And finally drying for 24h at 50 ℃ in vacuum to obtain the blue light organic electroluminescent material. The yield was 78%. Mass spectrum: m/z867.1 (M)++ 1); elemental analysis (%) C68H50Theoretical value: c94.19, H5.81; measured value: c94.27, H5.74.
FIG. 1 is a thermogravimetric analysis chart of a blue organic electroluminescent material prepared in example 1; thermogravimetric analysis was performed by a Perkin-Elmer Series7 thermoanalysis system, all measurements being performed in a room temperature atmosphere. From FIG. 1It can be seen that the thermal weight loss temperature (T) of the blue light organic electroluminescent material is 5%d) Is 411 ℃.
Example 2: the blue light organic electroluminescent material of the present example, i.e. 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene, was 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), 9- (4-pinacolboronic acid ester phenyl) -9-phenyl-9H-fluorene (293mg,0.66mmol) and 15mL of tetrahydrofuran were added into 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 sodium bicarbonate (3mL,2mol/L) solution 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 reaction, cooling to room temperature, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous magnesium sulfate, spin-drying, and separating the crude product with petroleum ether and ethyl acetate (10:1) as eluent by silica gel chromatography column to obtain white crystals. And finally drying for 24h at 50 ℃ in vacuum to obtain the blue light organic electroluminescent material. The yield was 74%.
。
Example 3: the blue light organic electroluminescent material of the present example, i.e. 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene, was prepared by the following steps:
under the protection of nitrogen, 9, 10-dibromo-2-tert-butylanthracene (118mg,0.3mmol), 9- (4-pinacolboronic acid ester phenyl) -9-phenyl-9H-fluorene (306mg,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 with nitrogen for about 30 min; the flask was heated to 130 ℃ for a Suzuki coupling reaction for 12 h. Stopping reaction, cooling to room temperature, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous magnesium sulfate, spin-drying, and separating the crude product with petroleum ether and ethyl acetate (10:1) as eluent by silica gel chromatography column to obtain white crystals. And finally drying for 24h at 50 ℃ in vacuum to obtain the blue light organic electroluminescent material. The yield was 82%.
Example 4: the blue light organic electroluminescent material of the present example, i.e. 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene, was prepared by the following steps:
9, 10-dibromo-2-tert-butylanthracene (118mg,0.3mmol), 9- (4-pinacolato boronate phenyl) -9-phenyl-9H-fluorene (320mg,0.72mmol), tris-bis-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, 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 120 ℃ for a Suzuki coupling reaction for 36 h. Stopping reaction, cooling to room temperature, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous magnesium sulfate, spin-drying, and separating the crude product with petroleum ether and ethyl acetate (10:1) as eluent by silica gel chromatography column to obtain white crystals. And finally drying for 24h at 50 ℃ in vacuum to obtain the blue light organic electroluminescent material. The yield was 80%.
Example 5:
this example 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. 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene (denoted by P).
As shown in fig. 2, the organic electroluminescent device has a structure including a conductive anode 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 conductive anode substrate; wherein:
the conductive anode substrate comprises a glass substrate and a conductive anode layer deposited on the surface of the glass substrate, wherein the conductive anode layer is made of Indium Tin Oxide (ITO), so the conductive anode substrate is also called ITO glass or is directly called ITO for short;
the material used as the hole injection layer is 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 light-emitting layer was 2-tert-butyl-9, 10-bis (4- (9-phenyl-9H-fluoren-9-yl) phenyl) anthracene;
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.
The specific method for manufacturing the organic electroluminescent device comprises the following steps:
spin-coating PEDOT (PSS) on the surface of a conductive anode layer (ITO) of the cleaned conductive anode substrate to prepare a hole injection layer;
then, a hole transport/electron blocking layer (TPD), a light emitting layer (P), an electron transport/hole blocking layer (BPhen), and an electron injection Layer (LiF) cathode layer (Al) were sequentially deposited on the surface of the hole injection layer.
The structure of the organic electroluminescent device can also be expressed as follows:
glass/ITO (150 nm)/PEDOT PSS (30nm)/TPD (40nm)/P (30 nm)/BPhen (35nm)/LiF (1.5nm)/Al (150 nm); wherein, the diagonal bars represent the laminated structure, and the numerical values in brackets are the thickness values of all functional layers.
The organic electroluminescent device was tested for current-luminance-voltage characteristics by a Keithley source measuring system (Keithley 2400source meter, Keithley2000 Cuirrentmeter) with a calibrated silicon photodiode, all measurements being made in a room temperature atmosphere. The test result shows that: the starting voltage of the device is 4.8V and is 1000cd/m2The lumen efficiency is 5.0 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 the blue-light organic electroluminescent material according to claim 5, wherein the mixture is a mixture of palladium acetate and tri-o-tolylphosphine, or 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 the blue light organic electroluminescent material according to claim 2, wherein the separating and purifying the reaction solution comprises:
after Suzuki coupling reaction is stopped, extracting with dichloromethane for multiple times, merging organic phases, drying the organic phases with anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product with a mixed eluent of petroleum ether and ethyl acetate in a 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. Use of the blue-emitting organic electroluminescent material according to claim 1 in the light-emitting layer of an organic electroluminescent device.
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