CN107011269A - Bipolarity small molecule emitter material using spiro fluorene unit as core of environmentally friendly solvent processing and preparation method and application can be used - Google Patents

Bipolarity small molecule emitter material using spiro fluorene unit as core of environmentally friendly solvent processing and preparation method and application can be used Download PDF

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CN107011269A
CN107011269A CN201710271283.7A CN201710271283A CN107011269A CN 107011269 A CN107011269 A CN 107011269A CN 201710271283 A CN201710271283 A CN 201710271283A CN 107011269 A CN107011269 A CN 107011269A
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core
unit
environmentally friendly
spiro fluorene
small molecule
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应磊
赵森
郭婷
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses bipolarity small molecule emitter material using spiro fluorene unit as core that can use environmentally friendly solvent processing and preparation method and application.Electrophilic unit and electron unit, by Suzuki coupling reactions, are connected to spiro fluorene unit both sides by the present invention using spiro fluorene unit as core, prepare the bipolarity small molecule emitter material using spiro fluorene unit as core that environmentally friendly solvent can be used to process.The bipolarity small molecule emitter material using spiro fluorene unit as core of the present invention has good dissolubility, film forming and film morphology stability in environmentally friendly solvent, there is good electronics and hole transport performance simultaneously, can be with the injection and transmission of equilbrium carrier, so that more electronics and hole are effectively combined and produce exciton, the mixing phenomena that luminescent layer based on the material can be avoided between hole/electric transmission bed boundary, so as to improve the luminous efficiency of device, and when preparing electroluminescent device without annealing so that preparation technology is simple.

Description

The bipolarity small molecule using spiro fluorene unit as core that environmentally friendly solvent can be used to process Luminescent material and preparation method and application
Technical field
The invention belongs to organic photoelectrical material field, and in particular to it is a kind of use environmentally friendly solvent process with spiro fluorene Unit is bipolarity small molecule emitter material of core and preparation method and application.
Background technology
Organic Light Emitting Diode (OLED) is because with efficient, low voltage drive, it is easy to which prepared by large area the advantages of obtains people Extensive concern.OLED research is started from the 1950s, until doctor Deng Qingyun of Kodak in 1987 adopts OLED luminosity under 10V direct voltage drives is have developed with sandwich device architecture and can reach 1000cd/m2, make OLED obtains epoch-making development.OLED is made up of the organic layer of negative electrode, anode and centre, and organic layer generally comprises electricity Sub- transport layer, luminescent layer and hole transmission layer, first electronics and hole inject from negative and positive the two poles of the earth respectively, and respectively in functional layer Migrated, then electronics and hole form exciton in place, exciton is migrated within the specific limits, last exciton It is luminous.
In order to realize the commercialization of organic/polymer electroluminescent device early, full color can be realized except that should meet Outside display, monochromatic purity are high, thermo-chemical stability is good and service life length etc. requires, it is also desirable to which device has high luminous effect Rate.One of principal element of influence OLED efficiency is the imbalance of material electronics in itself and hole transport injection at present. Therefore, in order to obtain efficient OLED, it is necessary to the balance of the electrons transmission and injection of reasonable adjusting material.In recent years Come, bipolar materials have attracted people extensive because of the hole with balance and electronic carrier stream in field of organic electroluminescence Concern, and the material causes the structure of device to simplify.This new technology is not only in theoretical research field by scientist Favored, and the production that progressively moving towards the industrialization, thus exploitation bipolar materials have practical value.
The content of the invention
It is an object of the invention to provide it is a kind of use environmentally friendly solvent process using spiro fluorene unit as the bipolar of core Property small molecule emitter material, the material has good electronics and hole transport performance, can be with the injection of equilbrium carrier and biography It is defeated so that more electronics and hole, which are effectively combined, produces exciton, so as to improve the luminous efficiency of device.
The present invention also aims to provide pair by core of spiro fluorene unit that environmentally friendly solvent can be used to process The preparation method of polar micromolecules luminescent material.
The present invention also aims to provide pair by core of spiro fluorene unit that environmentally friendly solvent can be used to process Application of the polar micromolecules luminescent material in the luminescent layer of organic electroluminescence device is prepared.
The purpose of the present invention is realized by following concrete technical scheme.
The bipolarity small molecule emitter material using spiro fluorene unit as core that environmentally friendly solvent can be used to process, with as follows Chemical structural formula：
In formula, Ar2For electrophilic unit, Ar1For electron unit；
In formula, R is-(CH2)k-O-(CH2)t- X, wherein, k=1-10, t=1-10, X is any one in following structure Kind：
Further, electrophilic unit Ar2For any one in following structure：
Wherein, n=1-3, R1For carbon number 1-20 straight chain or branched alkyl, or it is carbon number 1-20 alcoxyl Base.
Further, electron unit Ar1For any one in following structure：
Prepare the described luminous material of the bipolarity small molecule using spiro fluorene unit as core for using environmentally friendly solvent to process The method of material, comprises the following steps：
Using spiro fluorene unit as core, by Suzuki coupling reactions, electrophilic unit and electron unit are connected to spiro fluorene Unit both sides, obtain the luminous material of the bipolarity small molecule using spiro fluorene unit as core that environmentally friendly solvent can be used to process Material.
Further, the temperature of the Suzuki coupling reactions is 110~160 DEG C, and the time is 18~24 hours.
The described bipolarity small molecule emitter material using spiro fluorene unit as core for using environmentally friendly solvent to process should Luminescent layer for preparing organic electroluminescence device, pair by core of spiro fluorene unit that environmentally friendly solvent will can be used to process Polar micromolecules luminescent material is dissolved in environmentally friendly solvent, by spin coating, inkjet printing or printing film forming, obtains light-emitting diodes The luminescent layer of pipe；Light emitting diode based on the luminescent layer can be used for preparing flat-panel monitor.
Further, the environmentally friendly solvent includes ethanol, isopropanol, ethyl acetate or tetrahydrofuran.
Compared with prior art, the present invention has advantages below：
(1) centered on the present invention uses spiro fluorene unit first, bipolarity small molecule emitter material, and synthetic method have been synthesized Simply, it is easily purified, is conducive to industrial applications；
(2) the bipolarity small molecule emitter material using spiro fluorene unit as core of the invention has good in environmentally friendly solvent Good dissolubility, film forming and film morphology stability, and when preparing organic electroluminescence device without annealing so that Preparation technology is simple；
(3) there is the bipolarity small molecule emitter material using spiro fluorene unit as core of the invention good electronics and hole to pass Defeated performance, can be with the injection and transmission of equilbrium carrier so that more electronics and hole, which are effectively combined, produces exciton, is based on The mixing phenomena that the luminescent layer of the material can be avoided between hole/electric transmission bed boundary, so as to improve the luminous effect of device Rate.
Brief description of the drawings
Fig. 1 is the Thermal Chart of the bipolarity small molecule emitter material D1 using spiro fluorene unit as core；
Fig. 2 is the DSC spectrograms of the bipolarity small molecule emitter material D2 using spiro fluorene unit as core；
Fig. 3 is that ultraviolet-visibles of the bipolarity small molecule emitter material D3 under filminess using spiro fluorene unit as core is inhaled Receive spectrogram；
Fig. 4 is the luminescence generated by light spectrogram of the bipolarity small molecule emitter material D4 using spiro fluorene unit as core；
Embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention be not limited to Lower embodiment.
Embodiment 1
Compound M2 preparation
Under argon atmosphere, by the bromo- 3- oxapentanes (M1) (5.81g, 29.63mmol) of 1- amino -5- and 2,7- dibromo Spiro fluorene (5g, 9.88mmol) is added in dry two-mouth bottle, adds potassium hydroxide (2.77g, 49.39mmol), adds N, Dinethylformamide (DMF), is stirred at room temperature 16 hours, obtains compound M2.
Embodiment 2
Compound M3 preparation
Under argon atmosphere, compound M2 (5g, 6.79mmol) and benzimidazole boric acid (2.13g, 6.79mmol) are added Enter into two-mouth bottle, add 100ml toluene and be completely dissolved, add sodium carbonate (3.60g, 33.94mmol), the tetrabutyl Ammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (156.89mg, 135.77umol), react at 110 DEG C 18h；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate Dry；After solution concentration, (eluant, eluent selects petroleum ether/dichloromethane=6/1, v/v) is purified with silica gel column chromatography, is finally given White solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M3。
Embodiment 3
Using spiro fluorene unit as core bipolarity small molecule emitter material D1 preparation
Under argon atmosphere, compound M3 (5g, 5.40mmol) and triphenylamine borate (2.00g, 5.40mmol) are added Enter into two-mouth bottle, add 100mL toluene and be completely dissolved, add sodium carbonate (2.86g, 27.00mmol), the tetrabutyl Ammonium bromide (152.49mg, 967.86umol) and four triphenyl phosphorus palladiums (134.80mg, 108.00umol), react at 110 DEG C 18h；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate Dry；After solution concentration, (eluant, eluent selects petroleum ether/dichloromethane=6/1, v/v) is purified with silica gel column chromatography, is finally given White solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product D1。
Obtained bipolarity small molecule material D1 thermal multigraph is as shown in figure 1, it can be seen that the luminous material of small molecule Expect D1 decomposition temperature TdFor 456 DEG C, illustrate that small molecule emitter material D1 has good heat endurance.
Embodiment 4
The preparation of bipolarity small molecule emitter material D2 by core of spiro fluorene unit
Under argon atmosphere, M3 (5g, 5.40mmol) and carbazole (902.89mg, 5.40mmol) are added to 100mL two In mouth bottle, add 100mL toluene and be completely dissolved, add palladium (24.25mg, 108.00umol) and tri-tert phosphorus (43.7mg, 215.99umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, it is organic After layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent selection is purified with silica gel column chromatography Petroleum ether/dichloromethane=4/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and elementary analysis As a result the compound obtained by showing is target product.
The DSC spectrograms of bipolarity small molecule emitter material D2 by core of spiro fluorene unit are as shown in Fig. 2 can from figure Go out, in temperature-rise period, compound D2 does not observe obvious glass transition temperature.
Embodiment 5
2,7- diborate -9,9- dioctyl fluorenes
(1) by 2,7- dibromos fluorenes (10g, 30.86mmol), KOH (8.66g, 154.32mmol) is added to two mouthfuls of 250mL In bottle, add 100mL DMFs and be completely dissolved, is stirred at room temperature after 1 hour, it is disposable to add Bromooctane (17.88g, 92.59mmol), is stirred at room temperature 24 hours；It is extracted with ethyl acetate, organic layer is complete with saline solution After washing, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, is obtained Product is recrystallized with acetone, finally gives white solid.Yield 75%.1H NMR、13CNMR, MS and elementary analysis result Compound obtained by showing is target product, and preparation process chemical equation is as follows：
(2) under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 10.65mmol) of 2,7- bis- are dissolved in into 180mL to refine Tetrahydrofuran (THF) in, 1.6mol L are gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, then add 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, are warming up to Room temperature reaction 24 hours；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, Plus anhydrous magnesium sulfate is dried；After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection is purified with silica gel column chromatography Petrol ether/ethyl acetate=20/1, v/v), product is placed in refrigerator, obtains white solid, yield 70%.1H NMR、13CNMR、 Compound obtained by MS and elementary analysis result show is target product, and preparation process chemical equation is as follows：
Embodiment 6
Compound M4 preparation
Under an argon atmosphere, by the bromo- S of 2-, S- dioxydibenzes bithiophene (5g, 16.94mmol), 2- borates -9,9- bis- Octyl group fluorenes (21.77g, 33.88mmol), Na2CO3(8.98g, 84.70mmol) and TBAB 1g, is added to 250mL In two-mouth bottle, fully after dissolving, Pd (PPh are added3)4(391.51mg, 338.81umol), 16h is reacted at 110 DEG C；Use acetic acid Ethyl ester is extracted, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried；After solution concentration, carried with silica gel column chromatography Pure (eluant, eluent selects petroleum ether/dichloromethane=4/1, v/v), product is placed in refrigerator, obtains white solid, yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M4.
Embodiment 7
Compound M5 preparation
Under argon atmosphere, compound M2 (5g, 6.79mmol) and M4 (4.96g, 6.79mmol) are added to two-mouth bottle In, add 100ml toluene and be completely dissolved, add sodium carbonate (3.60g, 33.94mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (156.89mg, 135.77umol), 18h is reacted at 110 DEG C；Will Reactant mixture is poured into water, and is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried； After solution concentration, (eluant, eluent selects petroleum ether/dichloromethane=6/1, v/v) is purified with silica gel column chromatography, white is finally given Solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product M5.
Embodiment 8
Prepared by core bipolarity small molecule emitter material D3 of spiro fluorene unit
Under argon atmosphere, compound M5 (5g, 3.97mmol) and triphenylamine borate (1.70g, 4.59mmol) are added Enter into two-mouth bottle, add 100ml toluene and be completely dissolved, add sodium carbonate (2.10g, 19.83mmol), the tetrabutyl Ammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (91.67mg, 79.33umol), react at 110 DEG C 18h；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate Dry；After solution concentration, (eluant, eluent selects petroleum ether/dichloromethane=7/1, v/v) is purified with silica gel column chromatography, is finally given White solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.
Uv-visible absorption spectras of the bipolarity small molecule emitter material D3 under filminess by core of spiro fluorene unit Figure is as shown in figure 3, it can be seen that small molecule emitter material D3 maximum absorption band is located at 386nm.
Embodiment 9
The preparation of bipolarity small molecule emitter material D4 by core of spiro fluorene unit
Under argon atmosphere, compound M5 (5g, 3.97mmol) and carbazole (663.25mg, 3.97mmol) are added to two In mouth bottle, add 100mL toluene and be completely dissolved, add palladium (17.81mg, 79.33umol) and tri-tert Phosphine (32.10mg, 158.67umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, After organic layer is washed completely with saline solution, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent is purified with silica gel column chromatography Select petroleum ether/dichloromethane=5/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and element Compound obtained by analysis result shows is target product.
The luminescence generated by light spectrogram of bipolarity small molecule emitter material D4 by core of spiro fluorene unit is as shown in figure 4, from figure As can be seen that the photoluminescence spectra of bipolarity small molecule emitter material is located at 456nm.
Embodiment 10
The preparation of electroluminescent device based on small molecule
It is on 20 Ω/ tin indium oxide (ITO) glass, first successively with acetone, washing in the square resistance of well in advance Agent, deionized water and isopropanol are cleaned by ultrasonic, then plasma treatment 10 minutes；Spin coating, which is mixed, on ITO polystyrolsulfon acid Polyethoxy thiophene (PEDOT:PSS=1:1, w/w) film, thickness is 150nm；PEDOT:PSS films are 80 DEG C in vacuum drying oven Lower drying 8 hours；Then by the ethanol solution of bipolarity small molecule emitter material D1, D2, D3, D4 using alkyl phenanthrene unit as core (1wt%) is spin-coated on PEDOT respectively:The surface of PSS films, thickness is 80nm, is used as luminescent layer；Finally steamed successively on luminescent layer Plate the thick metal Al layers of a thin layer CsF (1.5nm) and 120nm.
The photo electric of electroluminescent device based on bipolarity small molecule emitter material D1~D4 using spiro fluorene unit as core Energy test result is as shown in table 1.
The photoelectric properties of electroluminescent device of the table 1 based on bipolarity small molecule emitter material D1~D4
As shown in Table 1, bipolarity small molecule emitter material D1, D2, D3 and D4 by core of spiro fluorene unit are based on device junction Structure：ITO/PEDOT/EML/CsF/Al maximum lumen efficiency is 1.5cd/A, 1.47cd/A, 2.0cd/A, 1.38cd/A, is had Higher luminous efficiency.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, it is other it is any without departing from Spirit Essences and the change made under principle of the present invention, modification, replacement, combine, simplification all should For equivalent substitute mode, it is included within protection scope of the present invention.

Claims (6)

1. the bipolarity small molecule emitter material using spiro fluorene unit as core that environmentally friendly solvent can be used to process, its feature exists In with following chemical structural formula：
In formula, Ar2For electrophilic unit, Ar1For electron unit；
In formula, R is-(CH2)k-O-(CH2)t- X, wherein, k=1-10, t=1-10, X is any one in following structure：
2. the bipolarity small molecule using spiro fluorene unit as core according to claim 1 for using environmentally friendly solvent to process Luminescent material, it is characterised in that electrophilic unit Ar2For any one in following structure：
Wherein, n=1-3；R1For carbon number 1-20 straight chain or branched alkyl, or it is carbon number 1-20 alkoxy；
Electron unit Ar1For any one in following structure：
3. the bipolarity using spiro fluorene unit as core for using environmentally friendly solvent to process prepared described in claim 1 or 2 is small The method of molecular ligh-emitting materials, it is characterised in that comprise the following steps：
Using spiro fluorene unit as core, by Suzuki coupling reactions, electrophilic unit and electron unit are connected to spiro fluorene unit Both sides, obtain the bipolarity small molecule emitter material using spiro fluorene unit as core that environmentally friendly solvent can be used to process.
4. the bipolarity small molecule using spiro fluorene unit as core according to claim 3 for using environmentally friendly solvent to process The preparation method of luminescent material, it is characterised in that the temperature of the Suzuki coupling reactions be 110~160 DEG C, the time be 18~ 24 hours.
5. use the bipolarity small molecule using spiro fluorene unit as core that environmentally friendly solvent is processed described in claim 1 or 2 Luminescent material is applied to prepare the luminescent layer of organic electroluminescence device, it is characterised in that can be added using environmentally friendly solvent The bipolarity small molecule emitter material using spiro fluorene unit as core of work is dissolved in environmentally friendly solvent, passes through spin coating, inkjet printing Or printing film forming, obtain the luminescent layer of light emitting diode.
6. application according to claim 5, it is characterised in that the environmentally friendly solvent includes ethanol, isopropanol, acetic acid Ethyl ester or tetrahydrofuran.
CN201710271283.7A 2017-04-24 2017-04-24 Bipolarity small molecule emitter material using spiro fluorene unit as core of environmentally friendly solvent processing and preparation method and application can be used Pending CN107011269A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019041847A1 (en) * 2017-08-30 2019-03-07 华南理工大学 Naphthothiodibenzofuran unit-based blue light polymer light-emitting material, preparation method therefor and use thereof
JP2019073489A (en) * 2017-10-19 2019-05-16 Dic株式会社 Organic electroluminescence element and material
CN111253332A (en) * 2018-11-30 2020-06-09 江苏三月光电科技有限公司 Organic compound, preparation method thereof and application of organic compound in OLED
WO2021120299A1 (en) * 2019-12-16 2021-06-24 深圳市华星光电半导体显示技术有限公司 Ink composition for ink-jet printing of organic light emitting diode and preparation method therefor
US11441045B2 (en) 2019-12-16 2022-09-13 Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Ink composition for inkjet printing organic light-emitting diodes and method of manufacturing the same

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Application publication date: 20170804