CN104178120A - Blue light phosphorescent host material containing benzimidazole unit, preparation method and organic electroluminescent device thereof - Google Patents
Blue light phosphorescent host material containing benzimidazole unit, preparation method and organic electroluminescent device thereof Download PDFInfo
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- CN104178120A CN104178120A CN201310204143.XA CN201310204143A CN104178120A CN 104178120 A CN104178120 A CN 104178120A CN 201310204143 A CN201310204143 A CN 201310204143A CN 104178120 A CN104178120 A CN 104178120A
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 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
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 tris-argon benzyl acetone Chemical compound 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
- 238000006069 Suzuki reaction reaction Methods 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
- 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 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
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 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
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims 1
- SROUTDZAHLYYOQ-UHFFFAOYSA-N [Ir]C=O.C1=CC=NC=C1 Chemical compound [Ir]C=O.C1=CC=NC=C1 SROUTDZAHLYYOQ-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 4
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- 239000010410 layer Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004090 dissolution Methods 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
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 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
- FIDLTJALOIOIEK-UHFFFAOYSA-N C(=O)[Ir+2].N1=CC=CC=C1 Chemical compound C(=O)[Ir+2].N1=CC=CC=C1 FIDLTJALOIOIEK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical group Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- PKXRXKHQSDBZQX-UHFFFAOYSA-N 3,6-dihydro-2H-[1,3]thiazolo[3,4-b][1,4,2]dioxazine Chemical compound C1ON2CSC=C2OC1 PKXRXKHQSDBZQX-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- ZHMKOSWPOJFQTD-UHFFFAOYSA-N C(C1)CC=CC1C(c1c2)(c3cc(-c4cccc(-c5nc6ccccc6[n]5-c5ccccc5)c4)ccc3-c1ccc2-c1cc(-c2nc(cccc3)c3[n]2-c2ccccc2)ccc1)c(cc1)cc(c2c3cccc2)c1[n]3-c1ccccc1 Chemical compound C(C1)CC=CC1C(c1c2)(c3cc(-c4cccc(-c5nc6ccccc6[n]5-c5ccccc5)c4)ccc3-c1ccc2-c1cc(-c2nc(cccc3)c3[n]2-c2ccccc2)ccc1)c(cc1)cc(c2c3cccc2)c1[n]3-c1ccccc1 ZHMKOSWPOJFQTD-UHFFFAOYSA-N 0.000 description 1
- GFFMIXGEYYHLRJ-UHFFFAOYSA-N C(C12)C=CC=C1N=C(c1cc(-c(cc3C4(c5ccccc5)c(cc5c6ccccc66)ccc5[n]6-c5ccccc5)ccc3-c(cc3)c4cc3-c3cc(-c4nc5ccccc5[n]4-c4ccccc4)ccc3)ccc1)N2c1ccccc1 Chemical compound C(C12)C=CC=C1N=C(c1cc(-c(cc3C4(c5ccccc5)c(cc5c6ccccc66)ccc5[n]6-c5ccccc5)ccc3-c(cc3)c4cc3-c3cc(-c4nc5ccccc5[n]4-c4ccccc4)ccc3)ccc1)N2c1ccccc1 GFFMIXGEYYHLRJ-UHFFFAOYSA-N 0.000 description 1
- GOESLOMYCNITBY-UHFFFAOYSA-N CC(C1)(C1(C)OSc1cccc(C2=NC3=CC=CCC3(C)N2c2ccccc2)c1)O Chemical compound CC(C1)(C1(C)OSc1cccc(C2=NC3=CC=CCC3(C)N2c2ccccc2)c1)O GOESLOMYCNITBY-UHFFFAOYSA-N 0.000 description 1
- FVXPNEZXAJEADX-UHFFFAOYSA-N Cc(cc1C(c2c3)(c4ccccc4)c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)ccc1-c2ccc3Br Chemical compound Cc(cc1C(c2c3)(c4ccccc4)c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)ccc1-c2ccc3Br FVXPNEZXAJEADX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of organic semiconductor materials, the invention discloses a blue light phosphorescent host material containing a benzimidazole unit, a preparation method and an organic electroluminescent device thereof. Specifically, the host material has a structural formula shown as the specification. The blue light phosphorescent host material containing the benzimidazole unit provided by the invention has a high triplet state energy level, and can effectively prevent back transmission of energy to the host material in a luminescence process, thus greatly improving the luminescence efficiency.
Description
Technical Field
The invention relates to the field of organic semiconductor materials, in particular to a blue light phosphorescence host material containing benzimidazole units and a preparation method thereof. The invention also relates to an organic electroluminescent device, wherein the luminescent layer material of the organic electroluminescent device comprises a blue phosphorescent host material containing benzimidazole units.
Background
The organic electroluminescent device has the advantages of low driving voltage, high response speed, wide visual angle range, abundant colors due to the fact that the luminous performance can be changed through fine adjustment of a chemical structure, high resolution, light weight, large-area panel display and the like, is known as a panel display technology in the 21 st century, and becomes a hotspot of research in the fields of materials, information, physics and other subjects and panel display. Future efficient commercial organic light emitting diodes will likely contain organometallic phosphors because they can trap both singlet and triplet excitons, achieving 100% internal quantum efficiency. However, due to the relatively long excited exciton lifetime of the transition metal complexes, unwanted triplet-triplet (T) results1-T1) Quenching in the actual operation of the device. To overcome this problem, researchers often dope triplet emitters into organic host materials.
In recent years, green and red phosphorescent OLED devices have exhibited satisfactory electroluminescent efficiency. While highly efficient blue phosphorescent devices are rare, the main reason is the lack of a combination of good carrier transport properties and high triplet energy level (E)T) The host material of (1).
Disclosure of Invention
One of the problems to be solved by the present invention is to provide a semiconductor device having a good carrier transport property and a high triplet level (E)T) The blue light phosphorescent host material containing the benzimidazole unit.
The second problem to be solved by the present invention is to provide a method for preparing a blue light phosphorescent host material containing a benzimidazole unit.
The invention also provides an organic electroluminescent device, wherein the luminescent layer material comprises a blue phosphorescent host material containing benzimidazole unit.
The technical scheme of the invention is as follows:
a blue light phosphorescence host material containing benzimidazole unit has the following structural formula:
namely, 3- (3- (9,9 '-spirobifluoren-2-yl) phenyl) -5- (3- (9,9' -spirobifluoren-7-yl) benzene) -4-phenyl-4H-1, 2, 4-triazole.
The preparation method of the blue light phosphorescence host material containing benzimidazole unit comprises the following steps:
compounds A and B are provided, respectively, represented by the following structural formulae,
i.e. 3- (2, 7-dibromo-9-phenyl-9H-fluoren-9-yl) -9-phenyl-9H-carbazole;
namely 1-phenyl-2- (3-pinacol boronate phenyl)) -1H-benzo [ d]Imidazole;
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 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 phosphorescence host material containing the benzimidazole unit with the following structural formula:
the preparation method of the blue light phosphorescence host material containing benzimidazole unit comprises the following steps that an oxygen-free environment is mainly composed of at least one gas of nitrogen and argon.
The preparation method of the blue light phosphorescence host material containing the benzimidazole unit comprises the following steps of (1) preparing a catalyst, 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 in the mixture, the molar weight of the organic phosphine ligand is 4-8 times that of the organic palladium; the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium; the organic phosphine ligand is tri-o-tolylphosphine or 2-dicyclohexyl phosphine-2 ', 6' -dimethoxy biphenyl;
the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
The preparation method of the blue light phosphorescence host material containing benzimidazole unit comprises the following steps of (1) selecting at least one of a sodium carbonate solution, a potassium carbonate solution and a sodium bicarbonate solution as the alkali solution; in the alkaline solution, the molar weight of the alkaline solute is 20 times of the molar weight of the compound A.
The preparation method of the blue light phosphorescence host material containing benzimidazole unit comprises the following steps of, wherein the organic solvent is at least one of toluene, N-dimethylformamide and tetrahydrofuran.
The preparation method of the blue-light phosphorescent main body material containing the benzimidazole unit comprises the following steps of performing Suzuki coupling reaction at the temperature of 90-120 ℃ for 24-36 hours.
The preparation method of the blue light phosphorescence host material containing benzimidazole unit comprises the following steps of:
after the coupling reaction is stopped, extracting the reaction liquid for a plurality of times, preferably more than three times, combining organic phases, drying the organic phases by anhydrous magnesium sulfate, then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit.
An organic electroluminescent device comprises a substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially stacked on one surface of the substrate; wherein, the material of each functional layer is as follows:
a substrate made of glass;
an anode layer made of Indium Tin Oxide (ITO) and combined with a glass substrate, which is generally called ITO glass or ITO;
a hole injection layer made of PEDOT (Poly ethylene glycol ether ketone) PSS (Poly ethylene glycol ether ketone);
a hole transport layer made of N, N '-bis [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl-4, 4' -diamine (NPD);
the material of the luminescent layer is a doped mixed material formed by adding bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (III) (FIrpic) into a blue light phosphorescence host material containing benzimidazole units with the following structural formula according to the mass percentage of 10 percent:
the electron transport layer is made of 8-hydroxyquinoline aluminum (Alq)3）
An electron injection layer of LiF, and
and the cathode layer is made of Al.
The blue light phosphorescence host material containing the benzimidazole unit provided by the invention has a high triplet state energy level, can effectively prevent energy from returning to the host material in a luminescence process, and greatly improves the luminescence efficiency; meanwhile, the blue light phosphorescence host material containing benzimidazole unit has better thermal stability.
In addition, the preparation method of the blue light phosphorescence host material containing the benzimidazole unit adopts a simpler synthesis 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 the blue phosphorescent host material containing a benzimidazole unit prepared in example 1.
Fig. 2 is a schematic view of the structure of an organic electroluminescent device produced in example 5.
Detailed Description
For a better understanding of the contents of the present patent application, the following further illustrates the technical scheme of the present invention by specific examples and illustrations, including materials preparation and device preparation, but these examples do not limit the present invention, wherein compound a, compound B are commercially available.
Example 1
The blue light phosphorescent host material containing benzimidazole unit, namely 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole, of the present example was prepared by the following steps:
under the protection of argon, adding 3- (2, 7-dibromo-9-phenyl-9H-fluorene-9-yl) -9-phenyl-9H-carbazole (128mg,0.2mmol) and 1-phenyl-2- (3-pinacol borate phenyl) -1H-benzo [ d ] imidazole (158mg,0.4mmol) into a flask containing 10mL of toluene solvent, fully dissolving, adding a potassium carbonate (2mL,2mol/L) solution into the flask, vacuumizing to remove oxygen and filling argon, and then adding bis (triphenylphosphine) palladium dichloride (5.6 mg,0.008 mmol); 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, combining 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 with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit. The yield was 80%.
Mass spectrum: m/z1019.4 (M)++ 1); elemental analysis (%) C75H49N5Theoretical value: c88.29, H4.84, N6.86; measured value: c88.36, H4.75, N6.90.
FIG. 1 is a thermogravimetric analysis chart of a blue phosphorescent host material containing a benzimidazole unit prepared in example 1; thermogravimetric analysis was performed by a Perkin-Elmer Series7 thermogravimetric analysis system, all measurements performed in a room temperature atmosphere, 5% thermogravimetric temperature (T.sub.w.)d) Is 455 ℃.
Example 2
The blue light phosphorescent host material containing benzimidazole unit, namely 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole, of the present example was prepared by the following steps:
under the protection of a mixed gas of nitrogen and argon, 3- (2, 7-dibromo-9-phenyl-9H-fluorene-9-yl) -9-phenyl-9H-carbazole (192mg,0.3mmol), 1-phenyl-2- (3-pinacol borate phenyl) -1H-benzo [ d ] imidazole (261mg,0.66mmol) and 15mL of tetrahydrofuran are added into a 50 mL-specification two-port bottle, after full dissolution, a mixed gas of nitrogen and argon is introduced to evacuate for about 20min, then tetratriphenylphosphine palladium (4 mg,0.003 mmol) is added, and after full dissolution, a sodium bicarbonate solution (3mL,2mol/L) is 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, combining 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 with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit. The yield was 84%.
Example 3
The blue light phosphorescent host material containing benzimidazole unit, namely 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole, of the present example was prepared by the following steps:
under the protection of nitrogen, 3- (2, 7-dibromo-9-phenyl-9H-fluoren-9-yl) -9-phenyl-9H-carbazole (192mg,0.3mmol), 1-phenyl-2- (3-pinacol borate phenyl) -1H-benzo [ d ] imidazole (285mg,0.72mmol), palladium acetate (3.5mg,0.015mmol) and tris (o-methoxyphenyl) phosphine (21mg, 0.06mmol) were added to a flask containing 12mL of N, N-dimethylformamide, and after sufficient dissolution, a solution of potassium carbonate (3mL,2mol/L) was added, and then the flask was purged 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, combining 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 with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit. The yield was 82%.
Example 4
The blue light phosphorescent host material containing benzimidazole unit, namely 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole, of the present example was prepared by the following steps:
3- (2, 7-dibromo-9-phenyl-9H-fluoren-9-yl) -9-phenyl-9H-carbazole (192mg,0.3mmol), 1-phenyl-2- (3-pinacol boronate phenyl) -1H-benzo [ d ] imidazole (285mg,0.72mmol), tris-dibenzylideneacetone 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, combining 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 with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit. The yield was 79%.
Example 5
This example is an organic electroluminescent device employing 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole prepared in any of examples 1 to 4 above as a host material of a light-emitting layer.
The organic electroluminescent device, as shown in fig. 2, includes a sequentially stacked structure: substrate 1/anode layer 2/hole injection layer 3/hole transport layer 4/light emitting layer 5/electron transport layer 6/electron injection layer 7/cathode layer 8; wherein slashes "/" indicate a layered structure.
The functional layer of the organic electroluminescent device is made of the following materials and the thickness:
the substrate 1 is made of glass;
the anode layer 2 is made of ITO (indium tin oxide compound) with the thickness of 150 nm; after the ITO is prepared on the surface of the glass, the ITO glass is called as the ITO glass for short;
the hole injection layer 3 is made of PEDOE (polymer ethylene terephthalate) PSS (polystyrene) and has the thickness of 30 nm; wherein PEDOT is poly 3, 4-ethylenedioxythiazole, PSS is a polystyrene-sulfonic acid composite material, and PEDOT and PSS are mixed of PEDOT and PSS;
the hole transport layer 4 was made of N, N '-bis [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl-4, 4' -diamine (NPD) and had a thickness of 20 nm;
the material of the light-emitting layer 5 is bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (III) (FIrpic) which is used as a guest light-emitting material, and is a doped mixed material obtained by doping 9-phenyl-3- (9-phenyl-2, 7-bis (3- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-9-yl) -9H-carbazole (represented by P) host material according to the mass ratio of 10%, wherein P is represented by FIrpic and the thickness is 20 nm;
the electron transport layer 6 is made of 8-hydroxyquinoline aluminum (Alq)3) The thickness is 30 nm;
the material of the electron injection layer 7 is lithium fluoride (LiF), and the thickness is 1.5 nm;
the cathode layer 8 is made of aluminum (Al) and has a thickness of 150 nm.
The organic electroluminescent device described above may be represented as:
glass/ITO/PEDOT PSS/NPD/P FIrpic/Alq3LiF/Al; wherein slashes "/" indicate a layered structure.
The preparation process of the organic electroluminescent device comprises the following steps:
firstly, preparing an ITO layer on the surface of cleaned glass through magnetron sputtering to obtain ITO glass;
secondly, moving the ITO glass into vacuum evaporation equipment, and spin-coating PEDOT (PSS) on the surface of the ITO layer;
finally, vapor plating NPD, P FIrpic and Alq are sequentially laminated on the surface of PEDOT and PSS3、LiF、Al；
And after the process steps are completed, obtaining the organic electroluminescent device.
The current-luminance-voltage characteristics of the organic electroluminescent device were performed by a Keithley source measuring system (Keithley 2400Sourcemeter, Keithley2000 Cuirrentmeter) with a calibrated silicon photodiode.
As a result of the test, the maximum current efficiency of the organic electroluminescent device was 6.9cd/A, and the maximum luminance was 17630cd/m2. The results show that the polymer main body material of the invention has better performanceIs good and is a blue light host material with great development prospect.
Claims (10)
1. A blue light phosphorescence host material containing benzimidazole unit is characterized in that the structural formula is as follows:
2. a preparation method of a blue light phosphorescence host material containing benzimidazole unit is characterized by 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 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 phosphorescence host material containing the benzimidazole unit with the following structural formula:
3. the preparation method of the benzimidazole unit-containing blue light phosphorescent host material as claimed in 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 method for preparing the blue-light phosphorescent host material containing the benzimidazole unit according to claim 2, wherein the catalyst is a mixture of organic palladium and organic phosphine ligands, and the molar amount of the organic phosphine ligands in the mixture is 4-8 times that of the organic palladium; the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
5. The method for preparing the blue-light phosphorescent host material containing the benzimidazole unit according to claim 4, wherein the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium; the organic phosphine ligand is tri-o-tolylphosphine or 2-dicyclohexyl phosphine-2 ', 6' -dimethoxy biphenyl.
6. 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 weight of the alkaline solute is 20 times of the molar weight of the compound A.
7. The method of claim 2, wherein the organic solvent is at least one of toluene, N-dimethylformamide, and tetrahydrofuran.
8. The method for preparing the blue-light phosphorescent host material containing the benzimidazole unit according to claim 2, wherein the Suzuki coupling reaction temperature is 90-120 ℃, and the reaction time is 24-36 hours.
9. The method for preparing a blue-light phosphorescent host material containing a benzimidazole unit according to claim 2, wherein the separating and purifying the reaction solution comprises:
after the coupling reaction is stopped, extracting the reaction liquid for multiple times by using dichloromethane, 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 with the volume ratio of 10:1 as eluent through a silica gel chromatographic column to obtain a crystal, and drying the crystal at 50 ℃ in vacuum for 24 hours to obtain the blue light phosphorescence host material containing the benzimidazole unit.
10. The organic electroluminescent device is characterized in that a luminescent layer of the organic electroluminescent device is made of bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium according to the mass percent of 10 percent and is added into a material with a structural formula ofThe blue light phosphorescence host material containing benzimidazole unitThe doped mixed material is formed.
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Cited By (5)
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