CN106866679A - It is a kind of that with two heteroaromatics, simultaneously indenes fluorenes unit is the bipolarity small molecule emitter material preparation method of core and applies - Google Patents
It is a kind of that with two heteroaromatics, simultaneously indenes fluorenes unit is the bipolarity small molecule emitter material preparation method of core and applies Download PDFInfo
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- 0 CC1C=C(c(cc(C(*)(*I)C(CC2(C)c3ccccc33)=C4C=C2S3(=O)=O)c4c2)c2S2(=O)=O)C2=CC1C Chemical compound CC1C=C(c(cc(C(*)(*I)C(CC2(C)c3ccccc33)=C4C=C2S3(=O)=O)c4c2)c2S2(=O)=O)C2=CC1C 0.000 description 6
- DASOKJSUOULVMM-UHFFFAOYSA-N CC1C=CC([n]2c(-c3ccc(C)cc3)nc3c2cccc3)=CC1 Chemical compound CC1C=CC([n]2c(-c3ccc(C)cc3)nc3c2cccc3)=CC1 DASOKJSUOULVMM-UHFFFAOYSA-N 0.000 description 1
- XQYDOBVMCSPRLI-UHFFFAOYSA-N Cc(cc1)ccc1S(c(cc1)ccc1-c1cc(-c2ccccc2)ccc1)(=O)=O Chemical compound Cc(cc1)ccc1S(c(cc1)ccc1-c1cc(-c2ccccc2)ccc1)(=O)=O XQYDOBVMCSPRLI-UHFFFAOYSA-N 0.000 description 1
- VKMOVPCGWDJHRS-SSEXGKCCSA-N Cc1cc(C(C[C@@H]2c3ccccc3)=Nc3c2cccc3)cc(C2=NC3=CCCC=C3N2c2ccccc2)c1 Chemical compound Cc1cc(C(C[C@@H]2c3ccccc3)=Nc3c2cccc3)cc(C2=NC3=CCCC=C3N2c2ccccc2)c1 VKMOVPCGWDJHRS-SSEXGKCCSA-N 0.000 description 1
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
The invention discloses a kind of with bipolarity small molecule emitter material that two heteroaromatics and indenes fluorenes unit are core and preparation method and application.The present invention is simple by the bipolarity small molecule emitter material synthetic method of core of two heteroaromatics and indenes fluorenes unit by the preparation of Suzuki coupling reactions, is easily purified, and is conducive to industrial applications.During the present invention is with two heteroaromatics and indenes fluorenes unit as the bipolarity small molecule emitter material of core, two heteroaromatics and indenes fluorenes flatness is preferably, with larger fluorescence quantum yield；Simultaneously, with good dissolubility, film forming and film morphology stability, solution processing and typographical display are appropriate for, for the preparation of the luminescent layer of Light-Emitting Diode, luminescent layer based on the bipolarity small molecule emitter material is when device is prepared without annealing so that preparation process is simple.
Description
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to a kind of with two heteroaromatics, simultaneously indenes fluorenes unit is core
Bipolarity small molecule emitter material 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.The research of OLED starts from the 1950's, until doctor Deng Qingyun of Kodak in 1987 adopts
OLED luminosity under 10V direct voltage drives is have developed with sandwich device architecture can reach 1000cdm-2, 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 electron transfer layer, luminescent layer
And hole transmission layer, electronics and hole inject from negative and positive the two poles of the earth respectively first, and are migrated in functional layer respectively, Ran Hou electricity
Son and hole form exciton in place, and exciton is migrated within the specific limits, last excitonic luminescence.
In order to realize the commercialization of organic/polymer electroluminescent device early, panchromatic showing can be realized except that should meet
Show, monochromatic purity is high, thermo-chemical stability is good and long service life etc. is required outward, it is also desirable to which device has luminous efficiency high.
One of principal element of influence OLED efficiency is the imbalance of material electronics in itself and hole transport injection at present.Cause
This, in order to obtain efficient OLED, it is necessary to the balance of electron hole transmission with the injection of reasonable adjusting material.
In recent years, bipolar materials are inhaled because of the hole with balance and electronic carrier stream in field of organic electroluminescence
Draw people widely to pay close attention to, and the material causes that the structure of device simplifies.This new technology is not only in theoretical research
Field is favored by scientist, and the production that progressively moving towards the industrialization, thus exploitation bipolar materials have practical valency
Value.
The content of the invention
It is an object of the invention to be directed to current existing problems faced, there is provided a kind of to be with two heteroaromatics and indenes fluorenes unit
The bipolarity small molecule emitter material of core.The material has good electronics and hole transport performance, can be with equilbrium carrier
Injection and transmission so that more electronics and hole are effectively combined and produce exciton, so as to improve the luminous efficiency of device.
The present invention also aims to provide it is described it is a kind of with two heteroaromatics and indenes fluorenes unit be the bipolarity small molecule of core
The preparation method of luminescent material.
The present invention also aims to provide it is described it is a kind of with two heteroaromatics and indenes fluorenes unit be the bipolarity small molecule of core
Application of the luminescent material in the luminescent layer for preparing light emitting diode.
A kind of with two heteroaromatics, simultaneously indenes fluorenes unit is the bipolarity small molecule emitter material of core, with following chemical constitution
Formula：
In formula, Ar is hexa-atomic heteroaromatic；Ar1It is electron donor unit；Ar2It is electron acceptor unit；
R be include halogen, cyano group, alkoxy, fluoroalkyl, H atom, aryl, triphenylamine, carbon number 1-20 it is straight
Chain or branched alkyl, or be the alkoxy of carbon number 1-20, or be-(CH2)k-O-(CH2)m- X, wherein, k=1-10, m
=1-10, X are any one in following structural formula：
Further, the Ar1It is any one in following structural formula：
Wherein, n=1-3；R1It is the straight chain or branched alkyl of carbon number 1-20, or is the alcoxyl of carbon number 1-20
Base.
Further, the Ar2It is any one in following structural formula：
It is described a kind of with two heteroaromatics and indenes fluorenes unit is the preparation method of the bipolarity small molecule emitter material of core, it is main
To include the preparation of the heteroaromatic of center cell two and indenes fluorenes.
It is described a kind of with two heteroaromatics and indenes fluorenes unit is the preparation method of the bipolarity small molecule emitter material of core, with
Simultaneously indenes fluorenes unit is core to two heteroaromatics, by Suzuki coupling reactions, by electron donor unit Ar1With electron acceptor unit Ar2Even
Two heteroaromatics and indenes fluorenes unit both sides are connected on, obtain described luminous by the bipolarity small molecule of core of two heteroaromatics and indenes fluorenes unit
Material.
Further, the temperature of the Suzuki coupling reactions is 110~160 DEG C, and the time of reaction is 16~18h.
It is described a kind of to be applied to prepare hair by the bipolarity small molecule emitter material of core of two heteroaromatics and indenes fluorenes unit
The luminescent layer of optical diode, by the bipolarity small molecule emitter material with organic solvent dissolve, by spin coating, inkjet printing or
Printing process film forming, obtains the luminescent layer of the Light-Emitting Diode.
Further, the organic solvent includes chlorobenzene.
Further, the luminescent layer can be used to prepare light emitting diode or flat-panel monitor.
Compared with prior art, the present invention has advantages below：
(1) centered on the present invention uses two heteroaromatics and indenes fluorenes first, bipolarity small molecule emitter material has been synthesized, and close
It is simple into method, it is easily purified, be conducive to industrial applications；
(2) bipolarity small molecule emitter material prepared by the present invention has good dissolubility, film forming and film morphology
Stability, is appropriate for solution processing and typographical display, and the luminescent layer based on the bipolarity small molecule emitter material is in preparing device
Without annealing during part so that preparation process is simple；
(3) during the present invention is with two heteroaromatics and indenes fluorenes unit as the bipolarity small molecule emitter material of core, two heteroaromatics are simultaneously
Indenes fluorenes flatness is preferable, with larger fluorescence quantum yield.
Brief description of the drawings
Fig. 1 is UV-visible absorption spectrums of the compound D1 under filminess；
Fig. 2 is photoluminescence spectra figures of the compound D2 under filminess；
Fig. 3 is photoluminescence spectra figures of the compound D3 under filminess；
Fig. 4 is the current density-luminous efficiency spectrogram of the electroluminescent device based on compound D4.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
The preparation of 2,7- dibromo fluorenes
In 250mL there-necked flasks, fluorenes (24.5g, 0.1mol), iron powder (88mg, 1.57mmol) and chloroform are added
100mL；Ice-water bath is cooled down, and bromine (17.6g, 0.1mol)/chloroform mixed solution 35mL is added dropwise, and temperature does not surpass in bottle during dropwise addition
Cross 5 DEG C；Reaction is finished, filtering, Gossypol recrystallized from chloroform, obtains white solid 20.3g, yield 83%.1HNMR、13CNMR, MS and element
Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 2
The preparation of 2,7- bis- bromo- 9,9- dioctyl fluorenes
Added in there-necked flask 2,7- dibromos fluorenes (9.7g, 0.03mol), benzyltriethylammoinium chloride (0.07g,
0.3mmol), dimethyl sulfoxide (DMSO) 90mL and 45mL sodium hydrate aqueous solutions (50wt%), at room temperature stirring form suspension；Add
1- bromines normal octane (12.5g, 65mmol), after continuing to stir 3 hours, are extracted with ether；Second is washed with saturated sodium-chloride water solution
Ether phase, anhydrous magnesium sulfate is dried；Solvent is boiled off, product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid.1H
NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.The following institute of chemical equation
Show：
Embodiment 3
2,7- diborate -9, the preparation of 9- dioctyl fluorenes
Under an argon atmosphere, bromo- 9, the 9- dioctyl fluorenes (5g, 9.12mmol) of 2,7- bis- are dissolved in the refined THF of 180mL
In, 1.6mol.L is gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, be subsequently adding 2- isopropoxy -4,4,
5,5- tetramethyl -1,3,2- dioxaborinate 25mL continue to react 1 hour at -78 DEG C, then heat to room temperature reaction 24 small
When；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate
Dry；After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selection petroleum ether/acetic acid second is purified with silica gel column chromatography
Ester=15/1, v/v), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR、13CNMR, MS and element
Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 4
The bromo- 2- quinoxalines methyl formates of 1-
Under an argon atmosphere, by bromo- 2- quinoxalines formic acid (10g, 39.73mmol) the addition two-mouth bottles of 1-, add
100mL methyl alcohol, is then added dropwise over the concentrated sulfuric acid (39.06mg, 397.29umol), is heated to 110 DEG C, reacts 18h；Reaction is mixed
Compound is poured into water, and is extracted with ethyl acetate, and after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；Solution is dense
After contracting, crude white solid is obtained, (eluant, eluent selects petroleum ether/dichloromethane=3/1, v/v) is purified with silica gel column chromatography, produced
Thing obtains white solid, yield 85% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis result show gained
The compound for arriving is target product.Chemical equation is as follows：
Embodiment 5
The preparation of compound M1
Under argon atmosphere, by 2,7- diborate -9,9- dioctyl fluorenes (5g, 7.78mmol) and the bromo- 2- naphthoic acids of 1-
Methyl esters (6.19g, 23.54mmol) is added in two-mouth bottle, is added 100ml toluene and is completely dissolved, and adds sodium carbonate
(4.12g, 38.91mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (179.84mg,
155.63umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer salt
After water is washed completely, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent selection petroleum ether/bis- are purified with silica gel column chromatography
Chloromethanes=8/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and elementary analysis result show
Resulting compound is target product.Chemical equation is as follows：
Embodiment 6
The preparation of compound M2
Under argon atmosphere, by M1 (10g, 13.07mmol) addition single port bottles, the anhydrous THF of 50ml are added until complete
CL；Reaction solution is reacted into 1h at 0 DEG C again, then is added dropwise over C8H17MgBr (n-octyl magnesium bromide), mixed liquor is in room temperature
Lower reaction 18h；Add water to that reaction is quenched in reaction solution, be extracted with ethyl acetate, organic layer saline solution is washed completely
Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether/dichloromethane=3/ is purified with silica gel column chromatography
1, v/v), product obtains white solid, yield 80% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis knot
Compound obtained by fruit shows is target product.Chemical equation is as follows：
Embodiment 7
The preparation of compound M3
Under argon atmosphere, M2 (5g, 8.58mmol) is dissolved in 50ml dichloromethane, trifluoro is added dropwise at room temperature
Change borate ether solution (588.67mg, 8.68mmol), react 18h；It is extracted with ethyl acetate, organic layer saline solution is washed completely
Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, product is for a long time
White solid, yield 90% are obtained in placement refrigerator.1H NMR、13CNMR, MS and elementary analysis result show resulting chemical combination
Thing is target product.Chemical equation is as follows：
Embodiment 8
The preparation of compound M4
Under argon atmosphere, M3 (5g, 4.38mmol) is dissolved in 50mL dichloromethane, add iron powder (185.35mg,
4.38mmol), then bromine (1.50g, 9.41mmol) is added dropwise over, 18h is reacted at room temperature；It is extracted with ethyl acetate, it is organic
After layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent selection is purified with silica gel column chromatography
Petroleum ether), yield 70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.Change
Learn reaction equation as follows：
Embodiment 9
The preparation of compound M5
Under an argon atmosphere, M4 (10g, 7.75mmol) is dissolved in the refined THF of 180mL, is gradually dripped at -78 DEG C
Plus the n-BuLi 32mL of 1.6mol L-1, react 2 hours, it is then quickly added into 2- isopropoxy -4,4,5,5- tetramethyl -1,
3,2- dioxaborinate 28mL, continue to react 1 hour at -78 DEG C, are to slowly warm up to room temperature reaction 24 hours；Reaction is mixed
Thing is poured into water, and is extracted with ethyl acetate, and after organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；Solution is concentrated
Afterwards, thick pale yellow shape crude product is obtained, (eluant, eluent selection petrol ether/ethyl acetate=20/1, v/ is purified with silica gel column chromatography
V), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR and GC-MASS test are shown to be target product
Thing.Chemical equation is as follows：
Embodiment 10
The preparation of compound M6
Under argon atmosphere, compound M4 (5g, 3.83mmol) and benzimidazole boric acid (1.23g, 3.83mmol) are added
Enter in two-mouth bottle, add 100ml toluene and be completely dissolved, add sodium carbonate (2.08g, 19.63mmol), the tetrabutyl
Ammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (190.73mg, 78.5umol), react at 110 DEG C
18h；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, 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, finally given
White solid, yield 80%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.
Chemical equation is as follows：
Embodiment 11
The preparation of compound D1
Under argon atmosphere, by compound M6 (1g, 683.51umol) and triphenylamine borate (253.77mg,
683.51umol) be added in two-mouth bottle, add 100ml toluene and be completely dissolved, add sodium carbonate (362.22mg,
3.42mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (15.08mg, 13.67umol),
18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer saline solution is washed completely
Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether/dichloromethane=6/ is purified with silica gel column chromatography
1, v/v) white solid, yield 80%, are finally given.1H NMR、13CNMR, MS and elementary analysis result show resulting change
Compound is target product.Chemical equation is as follows：
The compound D1 for obtaining under filminess UV-visible absorption spectrum as shown in figure 1, can from figure
Go out, absworption peaks of the compound D1 under filminess is located at 328nm and 398nm.
Embodiment 12
The preparation of compound D2
Under argon atmosphere, compound M6 (1g, 683.51umol) and carbazole (1114.29mg, 683.51umol) are added
Enter in 100ml two-mouth bottles, add toluene to be completely dissolved, add palladium (3.07mg, 13.67umol) and three tertiary fourths
Base phosphorus (5.53mg, 27.34umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate,
After organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent is purified with silica gel column chromatography
Selection petroleum ether/dichloromethane=4/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and element
Compound obtained by analysis result shows is target product.Chemical equation is as follows：
The compound D2 for obtaining under filminess photoluminescence spectra figure as shown in Fig. 2 it can be seen that chemical combination
Emission maximum spectrum of the thing D2 under filminess is in 456nm.
Embodiment 13
The preparation of compound M7
Under an argon atmosphere, by the bromo- S of 2-, S- dioxydibenzes bithiophene (5g, 16.94mmol), 2- borate -9,9- bis-
Octyl group fluorenes (21.77g, 33.88mmol), Na2CO3(8.98g, 84.70mmol) and TBAB 1g are 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, and after organic layer saline solution is washed completely, 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 obtains white solid, yield in placing refrigerator for a long time
70%.1H NMR、13Compound obtained by CNMR, MS and elementary analysis result show is target product.Chemical equation
It is as follows：
Embodiment 14
The preparation of compound M8
Under an argon atmosphere, by M4 (5g, 16.94mmol), M7 (21.77g, 33.88mmol), Na2CO3(8.98g,
84.70mmol) and TBAB 1g is added in 250ml two-mouth bottles, fully after dissolving, Pd (PPh are added3)4
(391.51mg, 338.81umol), 16h is reacted at 110 DEG C；It is extracted with ethyl acetate, organic layer saline solution is washed completely
Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether/dichloromethane=4/ is purified with silica gel column chromatography
1, v/v), product obtains white solid, yield 70% in placing refrigerator for a long time.1H NMR、13CNMR, MS and elementary analysis knot
Compound obtained by fruit shows is target product.Chemical equation is as follows：
Embodiment 15
The preparation of compound D3
Under argon atmosphere, by compound M8 (1g, 583.51umol) and triphenylamine borate (253.77mg,
583.51umol) be added in two-mouth bottle, add 100ml toluene and be completely dissolved, add sodium carbonate (362.22mg,
3.42mmol), TBAB (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (15.08mg, 13.67umol),
18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer saline solution is washed completely
Afterwards, plus anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether/dichloromethane=6/ is purified with silica gel column chromatography
1, v/v) white solid, yield 80%, are finally given.1H NMR、13CNMR, MS and elementary analysis result show resulting change
Compound is target product.Chemical equation is as follows：
The compound D3 for obtaining under filminess photoluminescence spectra figure as shown in figure 3, it can be seen that chemical combination
Emission maximum spectrum of the thing D3 under filminess is in 478nm.
Embodiment 16
The preparation of compound D4
Under argon atmosphere, compound M8 (1g, 583.51umol) and carbazole (1114.29mg, 583.51umol) are added
Enter in 100ml two-mouth bottles, add toluene to be completely dissolved, add palladium (3.07mg, 13.67umol) and three tertiary fourths
Base phosphorus (5.53mg, 27.34umol), 18h is reacted at 110 DEG C；Reactant mixture is poured into water, is extracted with ethyl acetate,
After organic layer saline solution is washed completely, plus anhydrous magnesium sulfate is dried；After solution concentration, (eluant, eluent is purified with silica gel column chromatography
Selection petroleum ether/dichloromethane=4/1, v/v), finally give white solid, yield 80%.1H NMR、13CNMR, MS and element
Compound obtained by analysis result shows is target product.Chemical equation is as follows：
Embodiment 17
The preparation of the electroluminescent device based on small molecule emitter material
It is on tin indium oxide (ITO) glass of 20 Ω/, acetone, washing first to be used successively in the square resistance of well in advance
Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；Spin coating is mixed on ITO polystyrolsulfon acid
Polyethoxy thiophene (mass ratio PEDOT:PSS=1:1) film, thickness is 150nm；PEDOT:PSS films are 80 DEG C in vacuum drying oven
Lower drying 8 hours；Then the chlorobenzene solution (1wt%) of bipolarity small molecule emitter material D1, D2, D3 and D4 is spin-coated on respectively
PEDOT:The surface of PSS films, thickness is 80nm, used as luminescent layer；Finally it is deposited with a thin layer CsF successively on luminescent layer
(1.5nm) and 120nm thick metal Al layer.
The structure of the electroluminescent device of preparation is ITO/PEDOT/EML/CsF/Al, the electroluminescent based on compound D4
Luminous efficiency-the current density plot of device is as shown in figure 4, figure 4, it is seen that the maximum lumen efficiency of device is
2.11cd/A。
Photoelectric properties to obtained each electroluminescent device are tested, as a result as shown in table 1.
Table 1 is based on the photoelectric properties index of the electroluminescent device of compound D1~D4
As shown in Table 1, compound D1, it is the electroluminescent of ITO/PEDOT/EML/CsF/Al that D2, D3 and D4 are based on device architecture
The maximum lumen efficiency of luminescent device is followed successively by 1.42cd/A, 1.77cd/A, 1.7cd/A, 2.11cd/A.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification all should
It is equivalent substitute mode, is included within protection scope of the present invention.
Claims (7)
1. a kind of with two heteroaromatics, simultaneously indenes fluorenes unit is the bipolarity small molecule emitter material of core, it is characterised in that with as follows
Chemical structural formula：
In formula, Ar is hexa-atomic heteroaromatic；Ar1It is electron donor unit；Ar2It is electron acceptor unit；
R be include halogen, cyano group, alkoxy, fluoroalkyl, H atom, aryl, triphenylamine, the straight chain of carbon number 1-20 or
Person's branched alkyl, or be the alkoxy of carbon number 1-20, or be-(CH2)k-O-(CH2)m- X, wherein, k=1-10, m=1-
10, X is any one in following structural formula：
2. it is according to claim 1 it is a kind of with two heteroaromatics and indenes fluorenes unit be the bipolarity small molecule emitter material of core,
Characterized in that, the electron donor unit Ar1It is any one in following structural formula：
Wherein, n=1-3；R1It is the straight chain or branched alkyl of carbon number 1-20, or is the alkoxy of carbon number 1-20.
3. it is according to claim 1 it is a kind of with two heteroaromatics and indenes fluorenes unit be the bipolarity small molecule emitter material of core,
Characterized in that, the electron acceptor unit Ar2It is any one in following structural formula：
4. a kind of luminous by the bipolarity small molecule of core of two heteroaromatics and indenes fluorenes unit described in any one of claims 1 to 3
The preparation method of material, it is characterised in that simultaneously indenes fluorenes unit is core with two heteroaromatics, by Suzuki coupling reactions, by electronics
Donor monomer Ar1With electron acceptor unit Ar2Be connected to two heteroaromatics and indenes fluorenes unit both sides, obtain it is described with two heteroaromatics simultaneously
Indenes fluorenes unit is the bipolarity small molecule emitter material of core.
5. it is according to claim 4 it is a kind of with two heteroaromatics and indenes fluorenes unit be the bipolarity small molecule emitter material of core
Preparation method, it is characterised in that the temperature of the Suzuki coupling reactions is 110~160 DEG C, the time of reaction is 16~18h.
6. a kind of with the luminous material of the bipolarity small molecule that two heteroaromatics and indenes fluorenes unit are core described in any one of claim 1-3
Material is applied to prepare the luminescent layer of light emitting diode, it is characterised in that by the bipolarity small molecule emitter material with organic molten
Agent is dissolved, and by spin coating, inkjet printing or printing process film forming, obtains the luminescent layer of the Light-Emitting Diode.
7. application according to claim 6, it is characterised in that the organic solvent includes chlorobenzene.
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| CN109957058A (en) * | 2017-12-26 | 2019-07-02 | 中国科学院长春应用化学研究所 | A kind of non-conjugated fluorescence polymer compound with space charge transfer effect and preparation method thereof, organic electroluminescence device |
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| CN101313047A (en) * | 2005-11-22 | 2008-11-26 | 葛来西雅帝史派有限公司 | Organic electroluminescent compounds and display device using the same |
| CN102372663A (en) * | 2010-08-20 | 2012-03-14 | 清华大学 | Pyridyl indenofluorene compound and application thereof |
| CN102782084A (en) * | 2010-03-06 | 2012-11-14 | 默克专利有限公司 | Organic electroluminescent device |
| CN105636944A (en) * | 2013-10-14 | 2016-06-01 | 默克专利有限公司 | Materials for electronic devices |
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| CN101313047A (en) * | 2005-11-22 | 2008-11-26 | 葛来西雅帝史派有限公司 | Organic electroluminescent compounds and display device using the same |
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