CN104629729A - Blue light organic electroluminescent material, preparation method and applications thereof - Google Patents
Blue light organic electroluminescent material, preparation method and applications thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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
- 238000001035 drying Methods 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
- 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
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- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- 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 9
- 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
- 150000001875 compounds Chemical class 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000012295 chemical reaction liquid Substances 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
- -1 tris-argon benzyl acetone Chemical compound 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
- KHNYNFUTFKJLDD-UHFFFAOYSA-N Benzo[j]fluoranthene Chemical compound C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000758 substrate Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 8
- OSQXTXTYKAEHQV-WXUKJITCSA-N 4-methyl-n-[4-[(e)-2-[4-[4-[(e)-2-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]ethenyl]phenyl]phenyl]ethenyl]phenyl]-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(\C=C\C=2C=CC(=CC=2)C=2C=CC(\C=C\C=3C=CC(=CC=3)N(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=2)=CC=1)C1=CC=C(C)C=C1 OSQXTXTYKAEHQV-WXUKJITCSA-N 0.000 description 7
- YONDEBNCTLTCRE-UHFFFAOYSA-N 7,12-diphenylbenzo[k]fluoranthene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C3=C4C=CC=C3C=CC=2)C4=C1C1=CC=CC=C1 YONDEBNCTLTCRE-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- QSOSWRKWWJSNLQ-UHFFFAOYSA-N 7,12-dibromobenzo[k]fluoranthene Chemical compound BrC1=C2C(=C(C=3C=4C=CC=C5C=CC=C(C13)C54)Br)C=CC=C2 QSOSWRKWWJSNLQ-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 239000007789 gas Substances 0.000 description 3
- 0 **c1ccccc1 Chemical compound **c1ccccc1 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical group C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 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
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XDACLRJRJBFXJD-UHFFFAOYSA-N C(=CC1=CC=CC=C1)C1=CC=CC=C1.C1=CC=CC=C1 Chemical class C(=CC1=CC=CC=C1)C1=CC=CC=C1.C1=CC=CC=C1 XDACLRJRJBFXJD-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- ZOXHPDJMUUCKNR-UHFFFAOYSA-N anthracene;9h-fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1.C1=CC=CC2=CC3=CC=CC=C3C=C21 ZOXHPDJMUUCKNR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 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
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Chemical group 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- JLAVCPKULITDHO-UHFFFAOYSA-N tetraphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JLAVCPKULITDHO-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic electroluminescent materials, and discloses a blue light organic electroluminescent material, a preparation method and applications thereof, wherein the structure formula of the material is defined in the instruction. According to the blue light organic electroluminescent material of the present invention, benzofluoranthene has high fluorescence quantum yield and good thermal stability, such that the emission energy of the blue light organic electroluminescent material is high, and the efficiency of the device based on the material is high.
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
Since the first reports of Organic Light Emitting Diodes (OLEDs) by c.w.tang et al, both small molecule and polymer light emitting diodes have had tremendous growth. Potential applications are full-color flat panel displays and solid-state white lighting. In three primary colors, both red and green diodes have approached the requirements of practical application, but the blue material has a larger carrier injection energy barrier due to a wider band gap and a lower highest occupied orbital (HOMO) energy level; meanwhile, the emission color is impure due to high and unstable emission energy and easy energy transfer, so the development is relatively slow. The development of blue light emitting materials with high efficiency and high stability performance is still a difficult problem.
In the development of materials, two ideas can be selected, namely, the novel blue phosphorescent material is developed, and the novel blue fluorescent material is developed. One advantage of fluorescent materials is that they are stable and do not decay as strongly as phosphorescent devices. Many novel blue fluorescent materials have been reported, such as: stilbene benzenes (DSA), beryllium pyridines, polyphenyl substituted benzenes, fluorenes, in particular spirofluorene derivatives, anthracene derivatives and fluorene anthracene hybrids. Recently, Lyu et al reported anthracene derivatives with tetraphenylsilicon as core, which have high glass transition temperature (T)g= 102-177 ℃), and has high color purity, the efficiency of a doped device is as high as 7.5cd/A, and the emission peak is 460 nm. Although many blue-emitting materials have been reported, few materials with high efficiency and stable emission properties have been reported.
Disclosure of Invention
The invention aims to solve the problems of the blue light organic electroluminescent material with good thermal stability and high luminous efficiency.
In order to achieve the purpose, the structure of the blue light organic electroluminescent material provided by the invention is as follows:
i.e. 7, 12-diphenylbenzo [ k ]]Fluoranthene.
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 tri-o-tolylphosphine, or 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 anode substrate, and a hole transport layer, a light emitting layer, an electron transport/hole blocking layer, an electron injection layer and a cathode layer which 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;
the material of the hole transport layer is N, N '-di [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl-4, 4' -diamine (NPD);
the material of the luminescent layer is the blue light organic electroluminescent material, namely a doped mixture formed by doping 3 mass percent of 4,4' -bis [4- (di-p-tolylamino) styryl ] biphenyl (DPAVBi) with 7, 12-diphenyl benzo [ k ] fluoranthene;
the material of the electron transport/hole blocking layer is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP);
the electron injection layer is made of LiF;
the cathode layer is made of Al.
The invention has the following advantages:
in the blue light organic electroluminescent material provided by the invention, benzofluoranthene has higher fluorescence quantum yield and good thermal stability, so that the organic blue light luminescent material has high emission energy, and the device efficiency based on the material is higher.
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 7, 12-diphenyl benzo [ k ] fluoranthene, is prepared by the following steps:
under the protection of argon, 7, 12-dibromobenzo [ k ]]Fluoranthene (82mg,0.2mmol) and phenylboronic acid (49mg,0.4mmol) are added into a flask containing 10mL of toluene solvent, potassium carbonate (2mL,2mol/L) solution is added into the flask after full dissolution, vacuum is pumped 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 100 ℃ 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 78%. Mass spectrum: m/z404.5 (M)++ 1); elemental analysis (%) C32H20Theoretical value: c95.02, H4.98; measured value: c95.14, H4.85.
FIG. 1 is a photograph obtained in example 1Thermogravimetric analysis graph of blue light 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) It was 390 ℃.
Example 2: the blue-light organic electroluminescent material of the embodiment has a structure of 7, 12-diphenyl benzo [ k ] fluoranthene, and is prepared by the following steps:
under the protection of a mixed gas of nitrogen and argon, 7, 12-dibromobenzo [ k ] fluoranthene (123mg,0.3mmol), phenylboronic acid (80.5mg,0.66mmol) and 15mL of tetrahydrofuran were put into a 50 mL-standard two-neck flask, and after fully dissolving, a mixed gas of nitrogen and argon was introduced to evacuate air 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 81%.
Example 3: the blue-light organic electroluminescent material of the embodiment has a structure of 7, 12-diphenyl benzo [ k ] fluoranthene, and is prepared by the following steps:
adding 7, 12-dibromobenzo [ k ] fluoranthene (123mg,0.3mmol), phenylboronic acid (88mg,0.72mmol), palladium acetate (3.5mg,0.015mmol) and tris (o-methylphenyl) phosphine (21mg, 0.06mmol) into a flask containing 12mL of N, N-dimethylformamide under the protection of nitrogen, adding a potassium carbonate (3mL,2mol/L) solution after sufficient dissolution, and then introducing nitrogen into the flask to evacuate air 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 86%.
Example 4: the blue-light organic electroluminescent material of the embodiment has a structure of 7, 12-diphenyl benzo [ k ] fluoranthene, and is prepared by the following steps:
7, 12-dibromobenzo [ k ] fluoranthene (123mg,0.3mmol), phenylboronic acid (88mg,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, 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 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 80%.
Example 5:
the embodiment is an organic electroluminescent device, and the host material of the luminescent layer is the blue light organic electroluminescent material prepared by the invention, namely 7, 12-diphenyl benzo [ k ] fluoranthene.
As shown in fig. 2, the organic electroluminescent device has a structure including a conductive anode substrate 1, and a hole transport layer 2, a light emitting layer 3, an electron transport/hole blocking layer 4, an electron injection layer 5, and a cathode layer 6 sequentially stacked on the conductive anode substrate; wherein:
the conductive anode substrate 1 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 of the hole transport layer 2 is N, N '-bis [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl-4, 4' -diamine (NPD);
the material of the light-emitting layer 3 is a doped mixture composed of 7, 12-diphenyl benzo [ k ] fluoranthene (expressed by P) as a host material and a guest material doped with 3 mass% of 4,4' -bis [4- (di-P-tolylamino) styryl ] biphenyl (DPAVBi), expressed as P: DPAVBi;
the material of the electron transport/hole blocking layer 4 is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP);
the electron injection layer 5 is made of LiF;
the cathode layer 6 is made of Al.
The specific method for manufacturing the electroluminescent device comprises the following steps:
and sequentially laminating a vapor deposition hole transport layer (NPD), a light emitting layer (P: DPAVBi), an electron transport/hole blocking layer (BCP), an electron injection Layer (LiF) and a cathode layer (Al) on the surface of the conductive anode layer (ITO) of the cleaned conductive anode substrate. The organic electroluminescent device can therefore also be represented as:
glass/ITO (150 nm)/NPD (20nm)/P is DPAVBi (20 nm)/BCP (30nm)/LiF (1.5nm)/Al (150 nm); wherein the diagonal bars indicate the layered structure, and the numerical values in parentheses are the thickness values of the respective functional layers.
The current-luminance-voltage characteristics of the organic electroluminescent device were wiped and the test was performed by a Keithley source measuring system (Keithley 2400Sourcemeter, Keithley2000 Cuirrentmeter) with a calibrated silicon photodiode, all measurements being performed in a room temperature atmosphere. The test result shows that: the starting voltage of the device is 4.3V and is 1000cd/m2The lumen efficiency is 3.6 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 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 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 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. 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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