CN104629734A - Blue light organic electroluminescence material containing silicon-fluorene unit, preparation method and application thereof - Google Patents
Blue light organic electroluminescence material containing silicon-fluorene unit, preparation method and application thereof Download PDFInfo
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- CN104629734A CN104629734A CN201310555012.6A CN201310555012A CN104629734A CN 104629734 A CN104629734 A CN 104629734A CN 201310555012 A CN201310555012 A CN 201310555012A CN 104629734 A CN104629734 A CN 104629734A
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- silafluorene
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical group [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000005401 electroluminescence Methods 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 10
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical group C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 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 16
- 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
- 239000000126 substance Substances 0.000 claims description 13
- 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
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 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
- 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
- 239000012295 chemical reaction liquid Substances 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
- 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
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- -1 tris-argon benzyl acetone Chemical compound 0.000 claims description 5
- 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 0 C[C@](C(*)C=C)NC Chemical compound C[C@](C(*)C=C)NC 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- SOODLDGRGXOSTA-UHFFFAOYSA-N 2-bromo-9-phenylcarbazole Chemical compound C=1C(Br)=CC=C(C2=CC=CC=C22)C=1N2C1=CC=CC=C1 SOODLDGRGXOSTA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 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
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 4
- 239000000872 buffer Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical group [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 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 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 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 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 description 1
- 239000012670 alkaline solution Substances 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
- 239000004305 biphenyl Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 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
- 239000003086 colorant Substances 0.000 description 1
- 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
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
The invention belongs to the field of organic electroluminescent device material, and discloses a blue light organic electroluminescence material containing a silicon-fluorene unit, a preparation method and an application thereof. A structural formula of the material is shown as follows. In the blue light organic electroluminescence material containing silicon-fluorene unit, carbazole is in a heterocyclic aromatic structure, has high triplet state energy level and hole mobility; silicon fluorene has high triplet state energy level, so that energy return on a main material during a luminescence process can be effectively avoided by the material, and the luminescence efficiency is greatly increased.
Description
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a blue light organic electroluminescent material containing a silicon fluorene unit, and a preparation method and application thereof.
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
The invention aims to provide a blue light organic electroluminescent material containing a silafluorene unit, which has higher carrier transport performance and triplet state energy level.
In order to achieve the purpose, the blue light organic electroluminescent material containing the silafluorene unit provided by the invention has the following structure:
i.e. 2,2' - (5, 5-dialkyl-5H-dibenzo [ b, d)]Silole-3, 7-diyl) bis (9-phenyl-9H-carbazole).
Another object of the present invention is to provide a method for preparing a blue-light organic electroluminescent material containing a silafluorene unit, which has a simple synthetic route, is cheap and easily available in materials, and comprises 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 containing the silicon fluorene unit with the following structural formula:
wherein the catalyst is bis-triphenylphosphine palladium dichloride or tetrakis triphenylphosphine palladium; or,
the catalyst is a mixture of organic palladium and an organic phosphine ligand, and the molar ratio of the organic palladium to the organic phosphine ligand is 1: 4-8; preferably, the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium, and the organic phosphine ligand is tris (o-methylphenyl) phosphine or 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl; more preferably, the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon benzylacetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
The molar ratio of the catalyst to the compound A is 1: 20-1: 100.
In the preparation method, the alkali solution is at least one selected from a sodium carbonate solution, a potassium carbonate solution and a sodium bicarbonate solution; in the alkaline solution, the molar ratio of the alkaline solute to the compound A is 20: 1.
In a preferred embodiment, the organic solvent is selected from at least one of toluene, N-dimethylformamide, tetrahydrofuran.
In a preferred embodiment, the reaction temperature of the Suzuki coupling reaction is 90-120 ℃, and the reaction time is 24-36 hours.
In a preferred embodiment, the separation and purification reaction liquid includes:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed 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 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 containing the silicon fluorene unit.
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 containing the silafluorene unit in a light-emitting layer of an organic electroluminescent device.
The organic electroluminescent device structurally comprises a conductive anode substrate, and a hole injection layer, a hole transmission/electron blocking layer, a light emitting layer, an electron transmission layer, an electron injection layer and a cathode layer which are sequentially stacked on the conductive anode substrate; 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 hole injection layer is made of PEDOT (PSS); the material of the hole transport/electron blocking 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 containing the silicon fluorene unit, namely, a doped mixture formed by doping 2,2' - (5, 5-dialkyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) di (9-phenyl-9H-carbazole) (expressed by P) with 11 mass percent of bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyliridium (FIrpic); the material of the electron transport layer is 8-hydroxyquinoline aluminum (Alq 3); the electron injection layer is made of LiF; the cathode layer is made of Al.
The invention has the following advantages:
(1) in the blue light phosphorescence host material containing the silafluorene unit, carbazole is of a nitrogen heteroaromatic ring structure and has high triplet state energy level and hole mobility; the silafluorene has higher triplet state energy level; therefore, the material effectively prevents energy from returning to the main material in the light emitting process, thereby greatly improving the light emitting efficiency.
(2) The blue light phosphorescence host material containing the silafluorene unit has good thermal stability.
The preparation method of the blue light organic electroluminescent material containing the silafluorene 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 a blue light organic electroluminescent material containing a silafluorene unit 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 containing a silafluorene unit, i.e., 2' - (5, 5-di-n-butyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) bis (9-phenyl-9H-carbazole), has the following structural formula:
the preparation process of the compound comprises the following steps:
under the protection of argon, 5, 5-di-n-butyl-3, 7-dipinacol boric acid ester-5H-dibenzo [ b, d]Silole (109mg,0.2mmol) and 2-bromo-9-phenyl-9H-carbazole (129mg,0.4mmol) were added to a flask containing 10mL of toluene solvent, after sufficient dissolution, a solution of potassium carbonate (2mL,2mol/L) was added to the flask, which was evacuated to remove oxygen and filled with waterArgon was added, followed by bis triphenylphosphine palladium dichloride (5.6 mg,0.008 mmol); the flask was heated to 120 ℃ for a Suzuki coupling reaction for 24 h. Stopping reaction, cooling to room temperature, 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 crude products, separating the crude products by using petroleum ether and ethyl acetate mixed leacheate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain crystal substances, and drying the crystal substances at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material containing the silafluorene unit. The yield was 78%. Mass spectrum: m/z777.1 (M)++ 1); elemental analysis (%) C56H48N2Theoretical value of Si: c8.55, H6.23, N3.60, si 3.61; measured value: c8.67, H6.15, N3.54, si3.62.
FIG. 1 is a thermogravimetric analysis chart of a blue light organic electroluminescent material containing a silafluorene unit prepared in example 1; thermogravimetric analysis was performed by a Perkin-Elmer Series7 thermoanalytical system, all measurements being performed in ambient atmosphere; as can be seen from FIG. 1, the thermal weight loss temperature (T) of the blue light organic electroluminescent material containing the silafluorene unit is 5%d) It was 381 ℃.
Example 2: the blue-light organic electroluminescent material of the embodiment has a structure of 2,2' - (5, 5-dimethyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) bis (9-phenyl-9H-carbazole), and is prepared by the following steps:
the preparation process of the compound comprises the following steps:
under the protection of a mixed gas of nitrogen and argon, adding 5, 5-dimethyl-3, 7-dipinacolone borate-5H-dibenzo [ b, d ] silole (139mg,0.3mmol), 2-bromo-9-phenyl-9H-carbazole (213mg,0.66mmol) and 15mL of tetrahydrofuran into a 50 mL-specification two-port bottle, fully dissolving, introducing a mixed gas of nitrogen and argon to exhaust air for about 20min, then adding tetratriphenylphosphine palladium (4 mg,0.003 mmol), fully dissolving, and then adding a sodium bicarbonate (3mL,2mol/L) solution. 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 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 crude products, separating the crude products by using petroleum ether and ethyl acetate mixed leacheate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain crystal substances, and drying the crystal substances at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material containing the silafluorene unit. The yield was 75%.
Example 3: the blue-light organic electroluminescent material of the embodiment has a structure of 2,2' - (5, 5-di-n-eicosyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) bis (9-phenyl-9H-carbazole), and is prepared by the following steps:
the preparation process of the compound comprises the following steps:
under the protection of nitrogen, adding 5, 5-di-N-eicosyl-3, 7-dipinacolone borate-5H-dibenzo [ b, d ] silole (299mg,0.3mmol), 2-bromo-9-phenyl-9H-carbazole (232mg,0.72mmol), palladium acetate (3.5mg,0.015mmol) and tri (o-methylphenyl) phosphine (21mg, 0.06mmol) into a flask containing 12mL of N, N-dimethylformamide, fully dissolving, adding a potassium carbonate (3mL,2mol/L) solution, and introducing nitrogen into the flask to exhaust air 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 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 crude products, separating the crude products by using petroleum ether and ethyl acetate mixed leacheate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain crystal substances, and drying the crystal substances at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material containing the silafluorene unit. The yield was 80%.
Example 4: the blue-light organic electroluminescent material of the embodiment has a structure of 2,2' - (5, 5-di-n-dodecyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) bis (9-phenyl-9H-carbazole), and is prepared by the following steps:
the preparation process of the compound comprises the following steps:
5, 5-di-N-dodecyl-3, 7-dipinacolone borate-5H-dibenzo [ b, d ] silole (232mg,0.3mmol), 2-bromo-9-phenyl-9H-carbazole (222mg,0.69mmol), tris-argon benzyl acetone 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 90 ℃ for a Suzuki coupling reaction for 36 h. Stopping reaction, cooling to room temperature, 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 crude products, separating the crude products by using petroleum ether and ethyl acetate mixed leacheate with the volume ratio of 10:1 through a silica gel chromatographic column to obtain crystal substances, and drying the crystal substances at 50 ℃ in vacuum for 24 hours to obtain the blue light organic electroluminescent material containing the silafluorene unit. The yield was 83%.
Example 5:
this example is an organic electroluminescent device, and the host material of the light-emitting layer is the bipolar blue-light phosphorescent host material prepared in the present invention, and preferably 2,2' - (5, 5-di-n-butyl-5H-dibenzo [ b, d ] silole-3, 7-diyl) bis (9-phenyl-9H-carbazole) prepared in example 1.
As shown in fig. 2, the organic electroluminescent device 300 has a structure including a substrate 301, an anode 302, a hole injection layer 303, a hole transport layer 304, a light emitting layer 305, an electron transport layer 306, an electron injection buffer layer 307, and a cathode 308.
In this embodiment, the substrate 301 is made of glass, an anode 302, a hole injection layer 303, a hole transport layer 304, a light emitting layer 305, an electron transport layer 306, an electron injection buffer layer 307, and a cathode 308 are sequentially vacuum-coated on the substrate 301, wherein the anode 302 is made of indium tin oxide with a sheet resistance of 10 to 20 Ω/□, the thickness of the indium tin oxide is 150nm, the hole injection layer 303 is made of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid, the thickness of the hole injection layer is 30nm, the hole transport layer 304 is made of N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1 ' -biphenyl-4, 4 ' -diamine, the thickness of the hole injection layer is 20nm, the light emitting layer 305 is made of 2,2' - (5, 5-di-N-butyl-5H-dibenzo [ b, d ] silol-3, 7-diyl) bis (9-phenyl-9H-carbazole), a guest luminescent material bis (4, 6-difluorophenylpyridine-N, C2) picolinoylated iridium (III) with a doping percentage of 11% based on the host material, a luminescent layer 305 having a thickness of 20nm, an electron transport layer 306 having a thickness of 30nm using Alq3, tris (8-hydroxyquinoline) aluminum, an electron injection buffer layer 307 using lithium fluoride having a thickness of 1.5nm, and a cathode 308 using metallic aluminum having a thickness of 150 nm.
The organic layer and the metal layer are deposited by thermal evaporation process with vacuum degree of 10-3～10-5pa, the thickness of the thin film adopts a film thickness monitorMonitor that all organic materials except the guest material have a vaporization rate ofSecond, the evaporation rate of lithium fluoride isThe evaporation rate of the metallic aluminum is
The electroluminescent device has high luminous efficiency and can be widely applied to the blue or white light emitting field. The current-luminance-voltage characteristics of the devices were all measured in a room temperature atmosphere using a Keithley source measurement system (Keithley 2400Sourcemeter, Keithley2000 Cuirrentmeter) with calibrated silicon photodiodes. The results show that: the starting voltage of the device is 3.8V and is 1000cd/m2The lumen efficiency is 6.5 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 containing a silafluorene unit is characterized in that the structure is as follows:
2. a method for preparing the blue light organic electroluminescent material containing the silafluorene unit as claimed in claim 1, which comprises 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 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 containing the silafluorene unit with the following structural formula:
3. the preparation method of the blue light organic electroluminescent material containing the silafluorene unit 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 containing the silafluorene unit 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 the blue-light organic electroluminescent material containing the silafluorene unit 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 containing the silafluorene unit according to claim 5, wherein the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon-benzyl-acetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
7. The method for preparing a blue light-emitting organic electroluminescent material containing a silafluorene unit according to 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 alkali solution, the molar ratio of an alkali solute to the compound A is 20: 1;
the organic solvent is at least one of toluene, N-dimethylformamide and tetrahydrofuran.
8. The preparation method of the blue-light organic electroluminescent material containing the silafluorene unit according to claim 2, wherein the reaction temperature of the Suzuki coupling reaction is 90-120 ℃, and the reaction time is 24-36 hours.
9. The method for preparing a blue light-emitting organic electroluminescent material containing a silafluorene unit according to any one of claims 2 to 7, wherein the separation and purification reaction solution comprises:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed leacheate 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 containing the silicon fluorene unit.
10. Use of the blue-emitting organic electroluminescent material containing a silafluorene unit according to claim 1 in a light-emitting layer of an organic electroluminescent device.
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| CN110590827B (en) * | 2019-09-30 | 2023-02-03 | 武汉天马微电子有限公司 | Organic electroluminescent compound and application thereof |
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