CN104293348A - Bipolar blue-light emitting host material, and preparation method and application thereof - Google Patents
Bipolar blue-light emitting host material, and preparation method and application thereof Download PDFInfo
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- CN104293348A CN104293348A CN201310306909.5A CN201310306909A CN104293348A CN 104293348 A CN104293348 A CN 104293348A CN 201310306909 A CN201310306909 A CN 201310306909A CN 104293348 A CN104293348 A CN 104293348A
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Abstract
The invention belongs to the field of organic semiconductor materials, and discloses a bipolar blue-light emitting host material, and a preparation method and an application thereof. The structural formula of the host material is shown in the specification. In the bipolar blue-light emitting host material, indoloacridinylcarbazole has a large planar rigid structure and is an excellent hole transport unit; and a diphenylphosphinosulfenyl group contains electron-withdrawing P=S, and is good electron transfer unit, so the material has hole transport and electron transfer properties to realize hole and electron transfer balance in a luminescent layer, and has a high triplet energy level to effectively prevent the return of energy to the host material in a luminescence process in order to substantially improve the luminescence efficiency.
Description
Technical field
The present invention relates to organic semiconductor material field, particularly relate to a kind of bipolarity Blue-light emitting host material and its preparation method and application.
Background technology
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view are wide and changes luminescent properties by chemical structure fine setting makes rich color, easily realize the advantages such as resolving power is high, lightweight, large-area flat-plate display, be described as " 21 century flat panel display ", become the focus of the subjects such as material, information, physics and flat pannel display area research.Following commercialization Organic Light Emitting Diode efficiently will contain organo-metallic phosphorescent substance possibly, because singlet and triplet excitons can all be caught by they, thus realize the internal quantum efficiency of 100%.But, because the excited state exciton lifetime of transition metal complex is relatively long, cause unwanted triplet state-triplet state (T
1-T
1) cancellation in device real work.In order to overcome this problem, triplet emission thing is often doped in organic host material by investigators.
In recent years, green and red phosphorescent OLED shows gratifying electroluminescent efficiency.And blue phosphorescent device is little efficiently, simultaneously major cause lacks to have good carrier transmission performance and higher triplet (E
t) material of main part.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of carrier transmission performance and higher triplet and the high bipolarity Blue-light emitting host material of luminous efficiency.
Technical scheme of the present invention is as follows:
A kind of bipolarity Blue-light emitting host material provided by the invention, its general structure is as follows:
i.e. 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine.
Another object of the embodiment of the present invention is the preparation method providing a kind of bipolarity Blue-light emitting host material, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
A:
i.e. 8-phenyl-8-(4-(tetramethyl ethylene ketone boric acid ester) phenyl)-8H-indoles also [3,2,1-de] acridine;
B:
i.e. (4-bromophenyl) diphenylphosphine sulphur;
Under oxygen-free environment (oxygen-free environment of at least one gas composition in preferred argon gas, nitrogen), be after dissolving during the compd A of 1:1 ~ 1.2 and B are added into containing catalyzer and alkaline solution organic solvent by mol ratio, Suzuki coupling reaction is carried out 12 ~ 48 hours at 70 ~ 130 DEG C, polyreaction is stopped after cooling, through separating-purifying reaction solution, obtain the described bipolarity Blue-light emitting host material of following general structure:
Wherein, described catalyzer is described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; Or
Palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture;
The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
Described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and in described alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
In a preferred embodiment, organic solvent is selected from solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
In a preferred embodiment, Suzuki coupling reaction at 90 ~ 120 DEG C, reaction within 24 ~ 36 hours, carry out.
In a preferred embodiment, separating-purifying reaction solution comprises step:
After reaction stops, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.
The present invention also provides a kind of above-mentioned bipolarity Blue-light emitting host material in organic electroluminescence device as the application of emitting layer material.
In bipolarity Blue-light emitting host material of the present invention, indoles acridine carbazole has large plane rigid structure is a good hole transporting unit; Diphenyl phosphine methylthio group contains electrophilic P=S, is a good electric transmission unit; Therefore this material has hole transport character and electronic transport property simultaneously, and the transmission of hole and electronics in luminescent layer is balanced, and this material also has higher triplet, effectively prevents energy in luminescence process from returning to material of main part; Therefore, this material can improve luminous efficiency greatly.In addition, the thermostability of this material is higher.
The preparation method of above-mentioned bipolarity Blue-light emitting host material, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And obtained polymeric material constructions is novel, solubility property is good, and film forming properties is excellent, is applicable to organic electroluminescence device.This material has higher electroluminescent efficiency.
Accompanying drawing explanation
Fig. 1 is the thermogravimetic analysis (TGA) figure of the bipolarity Blue-light emitting host material that embodiment 1 obtains;
Fig. 2 is the structural representation of the organic electroluminescence device that embodiment 5 obtains.
Embodiment
In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein compd A and B all commercially obtain.
Embodiment 1:
The bipolarity Blue-light emitting host material of the present embodiment, its structure is 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine, and preparation process is as follows:
Under argon shield, 8-phenyl-8-(4-(tetramethyl ethylene ketone boric acid ester) phenyl)-8H-indoles also [3,2,1-de] acridine (107mg, 0.2mmol), (4-bromophenyl) diphenylphosphine sulphur (75mg, 0.2mmol) add in the flask filling 10ml toluene solvant, by salt of wormwood (2mL after abundant dissolving, 2mol/L) solution joins in flask, vacuumize deoxygenation and be filled with argon gas, then bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol) is added; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 24h.Stopped reaction cool to room temperature, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.Productive rate is 83%.Mass spectrum: m/z699.2(M
++ 1); Ultimate analysis (%) C
49h
34nPS: theoretical value C84.09, H4.90, N2.00, P4.43, S4.58; Measured value C84.16, H4.83, N2.07, P4.40, S4.54.
Fig. 1 is the thermogravimetic analysis (TGA) figure of the bipolarity Blue-light emitting host material that embodiment 1 obtains; Wherein, thermogravimetic analysis (TGA) is completed by the measurement of Perkin-Elmer Series7 Thermo System, and all measurements all complete in atmosphere at room temperature.As shown in Figure 1, the thermal weight loss temperature (T of bipolarity Blue-light emitting host material 5%
d) be 383 DEG C.
Embodiment 2:
The bipolarity Blue-light emitting host material of the present embodiment, its structure is 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine, and preparation process is as follows:
Under nitrogen and argon gas gas mixture are protected; by 8-phenyl-8-(4-(tetramethyl ethylene ketone boric acid ester) phenyl)-8H-indoles also [3; 2; 1-de] acridine (160mg; 0.3mmol), (4-bromophenyl) diphenylphosphine sulphur (123mg; 0.33mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein; sodium bicarbonate (3mL, 2mol/L) solution is added again after abundant dissolving.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Suzuki coupling reaction 48h.Stopped reaction cool to room temperature, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.Productive rate is 86%.
Embodiment 3:
The bipolarity Blue-light emitting host material of the present embodiment, its structure is 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine, and preparation process is as follows:
Under nitrogen protection, by 8-phenyl-8-(4-(tetramethyl ethylene ketone boric acid ester) phenyl)-8H-indoles also [3,2,1-de] acridine (160mg, 0.3mmol), (4-bromophenyl) diphenylphosphine sulphur (135mg, 0.36mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join the N filling 12mL, in the flask of dinethylformamide, salt of wormwood (3mL, 2mol/L) solution is added, after logical nitrogen purge gas is about 30min in flask subsequently after abundant dissolving; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.Productive rate is 85%.
Embodiment 4:
The bipolarity Blue-light emitting host material of the present embodiment, its structure is 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine, and preparation process is as follows:
Under nitrogen protection; by 8-phenyl-8-(4-(tetramethyl ethylene ketone boric acid ester) phenyl)-8H-indoles also [3; 2; 1-de] acridine (160mg; 0.3mmol), (4-bromophenyl) diphenylphosphine sulphur (135mg; 0.36mmol), three or two argon benzyl acetone two palladium (9mg; 0.009mmol) with 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N filling 12mL; in the flask of dinethylformamide, after fully dissolving, add sodium carbonate (3mL, 2mol/L) solution.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 36h.Stopped reaction cool to room temperature, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.Productive rate is 82%.
Embodiment 5:
The present embodiment is organic electroluminescence device, its luminescent layer adopts the arbitrary obtained bipolarity Blue-light emitting host material of embodiment 1 to 4, i.e. 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] acridine is as the material of main part of luminescent layer.
As shown in Figure 2, this organic electroluminescence device comprises the structure stacked gradually: conductive substrate layer 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, cathode layer 7; Wherein, the material of each functional layer and thickness as follows:
Conductive substrate layer 1 comprises substrate, and is deposited on the anode layer of substrate surface; In the present embodiment, the material of substrate is preferably glass, and the material of anode layer is indium tin oxide (ITO), and itself and glass combine, and is called for short ito glass, and conventional ITO replaces; The thickness of ITO is 150nm;
The material of hole injection layer 2 is poly-3,4-ethylenedioxy thiazoles (PEDOT) and the mixture of polystyrene-sulfonic acid matrix material (PSS), is expressed as PEDOT:PSS; The thickness of hole injection layer 2 is 30nm;
The material of hole transmission layer 3 is N, N '-two [(1-naphthyl)-N, N '-phenylbenzene]-1,1 '-xenyl-4,4 '-diamines (NPD), and the thickness of hole transmission layer 3 is 30nm.
The material of luminescent layer 4 is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (III) (FIrpic) according to the obtained multipolymer Blue-light emitting host material of the embodiment 1 that is doped to of mass percent of 10%, i.e. 8-(4'-(diphenylphosphine sulphur) phenylbenzene-4-base)-8-phenyl-8H-indoles also [3,2,1-de] the middle dopant mixture formed of acridine (representing with P1); Be expressed as P1:FIrpic; The thickness of luminescent layer 4 is 20nm;
The material of electron transfer layer 5 is three-oxine aluminium (Alq
3), the thickness of electron transfer layer 5 is 30nm;
The material of electron injecting layer 6 is LiF; The thickness of electron injecting layer 6 is 1.5nm;
The material of cathode layer 7 is aluminium, and the thickness of cathode layer 7 is 150nm.
The structure of this organic electroluminescence device can be expressed as:
Ito glass/PEDOT:PSS/NPD/P1:FIrpic/Alq
3/ LiF/Al; Wherein, brace "/" represents laminate structure.
The concrete grammar that this organic electroluminescence device makes is:
Spin coating PEDOT:PSS successively on conductive glass (ITO) substrate through cleaning, evaporation NPD, P1:FIrpic, Alq successively on its surface again after to be dried
3, LiF, Al, obtained organic electroluminescence device.
In room temperature, air, adopt Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correcting silicon photoelectric diode, electroluminescent spectrum, by French JY company SPEX CCD3000 spectrometer measurement, carries out current versus brightness-voltage characteristic to the organic electroluminescence device of preparation and measures; Test result shows, and the trigger voltage of this organic electroluminescence device is 3.6V, at 1000cd/m
2brightness under, luminous efficiency is 7.7lm/W.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a bipolarity Blue-light emitting host material, is characterized in that, its general structure is as follows:
2. a preparation method for bipolarity Blue-light emitting host material, is characterized in that, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be dissolve mol ratio during the compd A of 1:1 ~ 1.2 and B are added into containing catalyzer and alkaline solution organic solvent, Suzuki coupling reaction is carried out 12 ~ 48 hours at 70 ~ 130 DEG C, polyreaction is stopped after cooling, separating-purifying reaction solution, obtains the described bipolarity Blue-light emitting host material of following general structure:
3. the preparation method of bipolarity Blue-light emitting host material according to claim 2, is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
4. the preparation method of bipolarity Blue-light emitting host material according to claim 2, it is characterized in that, palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
5. the preparation method of bipolarity Blue-light emitting host material according to claim 2, is characterized in that, described alkaline solution is at least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution; In described alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
6. the preparation method of bipolarity Blue-light emitting host material according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
7. the preparation method of bipolarity Blue-light emitting host material according to claim 2, is characterized in that, Suzuki coupling reaction at 90 ~ 120 DEG C, reaction within 24 ~ 36 hours, carry out.
8. the preparation method of bipolarity Blue-light emitting host material according to claim 2, is characterized in that, separating-purifying reaction solution comprises step:
After reaction stops, with methylene dichloride repeatedly extractive reaction liquid, obtain organic phase and merge organic phase, then crude product is obtained with being spin-dried for organic phase after anhydrous magnesium sulfate drying, crude product employing volume ratio is that the sherwood oil of 10:1 is leacheate with ethyl acetate mixtures and is separated through silica gel column chromatography to obtain crystal, this crystal, after 50 DEG C of dry 24h under vacuo, obtains described bipolarity Blue-light emitting host material.
9. a bipolarity Blue-light emitting host material as claimed in claim 1 in organic electroluminescence device as the application of emitting layer material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709330A (en) * | 2015-11-17 | 2018-02-16 | 株式会社Lg化学 | Spiro-compound and the organic illuminating element for including it |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709330A (en) * | 2015-11-17 | 2018-02-16 | 株式会社Lg化学 | Spiro-compound and the organic illuminating element for including it |
| CN107709330B (en) * | 2015-11-17 | 2020-03-27 | 株式会社Lg化学 | Spiro compound and organic light-emitting element comprising same |
| US11050026B2 (en) | 2015-11-17 | 2021-06-29 | Lg Chem, Ltd. | Spiro compound and organic light-emitting element comprising same |
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Application publication date: 20150121 |