CN110016053A - The soluble pyridine derivatives of Asymmetrical substitute and preparation, n- doping electron transfer layer and application - Google Patents
The soluble pyridine derivatives of Asymmetrical substitute and preparation, n- doping electron transfer layer and application Download PDFInfo
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Abstract
The invention belongs to the technical fields of small organic molecule functional material, disclose soluble pyridine derivatives and preparation, the n- doping electron transfer layer and application of Asymmetrical substitute.The soluble pyridine derivatives of the Asymmetrical substitute are more than one in Formulas I or Formula II.The invention also discloses the preparation methods of the soluble pyridine derivatives of Asymmetrical substitute.The soluble pyridine derivatives of the Asymmetrical substitute are used to prepare Organic Electron Transport Material.The Organic Electron Transport Material includes more than one in the soluble pyridine derivatives of above-mentioned Asymmetrical substitute.The n- doping electron transfer layer is to adulterate to obtain by n- by Organic Electron Transport Material.Organic Electron Transport Material of the invention electron mobility with higher is formed by electron transfer layer by n- doping, is used for organic electroluminescence device, has high-luminous-efficiency and high stability.The application of n- doping electron transfer layer of the invention in organic electroluminescence device.
Description
Technical field
The invention belongs to the technical fields of small organic molecule functional material, are related to electron transport material, and in particular to a kind of
Soluble pyridine derivatives of Asymmetrical substitute and preparation method thereof, n- doping electron transfer layer and application.The asymmetry
Substituted soluble pyridine derivatives are used for Organic Electron Transport Material, and by by the soluble pyridines of Asymmetrical substitute
Derivative carries out n- doping and obtains n- doping electron transfer layer.The organic electron transport layer, n- doping electron transfer layer are having
Application in machine light emitting diode.
Background technique
Organic Light Emitting Diode (OLEDs) has important application in electroluminance display and lighting area.Wherein, electric
Sub- transmission material is most important for Organic Light Emitting Diode, and electronics is assisted from cathode to be injected into luminescent layer, and obstruct electrode with
Luminescent layer directly contacts.In general, design high-purity, high-performance OLED electron transport material are challenging, need to consider many
Factor and its between complicated trade-off relationship, as glass transition temperature, carrier mobility, triplet energy level, electron injection and
Hole-blocking characteristics.Wherein, for the pursuit of high mobility, electron transport material indissoluble is often led to, not easy purification.In addition close
Phase studies have shown that in electron transport material, even if micro halide end group remains, the stability of OLED device will also be produced
Raw fatal influence (H.Fujimoto etc., Influence of material impurities in the hole-
blocking layer on the lifetime of organic light-emitting diodes,
Appl.Phys.Lett.2016, volume 109).
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of soluble pyridines of Asymmetrical substitute
Analog derivative and preparation method thereof.The soluble pyridine derivatives of Asymmetrical substitute of the invention prepare simple and solvable, tool
There is high glass transition temperature, be used as Organic Electron Transport Material, can get high efficiency, high stable organic electroluminescence device.
Another object of the present invention is to provide the applications of the soluble pyridine derivatives of above-mentioned Asymmetrical substitute.It is described
The soluble pyridine derivatives of Asymmetrical substitute are used to prepare Organic Electron Transport Material.The Organic Electron Transport Material,
For more than one in the soluble pyridine derivatives of above-mentioned Asymmetrical substitute.Organic Electron Transport Material of the invention has height
Glass transition temperature is used to prepare electronic device, can get high efficiency, high stable organic electroluminescence device.
A further object of the present invention is to provide a kind of n- to adulterate electron transfer layer.The n- doping electron transfer layer is benefit
It is adulterated and is obtained by n- with above-mentioned Organic Electron Transport Material.Small organic molecule electron transport material provided by the present invention, warp
N- doping, has high electron mobility.
A further object of the present invention is to provide above-mentioned n- doping electron transfer layers to answer in the devices such as organic electroluminescent
With.
The purpose of the present invention is achieved through the following technical solutions:
A kind of soluble pyridine derivatives of Asymmetrical substitute are more than one in following formula I or Formula II:
The preparation method of the soluble pyridine derivatives of the Asymmetrical substitute, comprising the following steps:
(1) under the action of n-BuLi, diphenyl phosphine chloride is reacted, subsequent processing with phenyl-dihalide, obtains non-oxygen
The brominated intermediate product changed；The phenyl-dihalide is m-dibromobenzene, diiodo-benzene or the bromo- 3- iodobenzene of 1-；
The structure of the unoxidized brominated intermediate product is
(2) hydrogen peroxide oxidation processing step (1) resulting unoxidized brominated intermediate product is used, subsequent processing obtains
The brominated intermediate product of oxidation；
The structural formula of the brominated intermediate product of the oxidation is
(3) under the action of palladium catalyst, the brominated intermediate product of step (2) resulting oxidation and bis (pinacolato) diboron is anti-
It answers, obtains the intermediate product containing borate；
The structure of the intermediate product containing borate is
(4) by the effect of palladium catalyst, by the intermediate product and 2 of the resulting boracic acid esters of step (3), 6- dibromo pyridine
Coupling reaction is carried out, the bromide containing pyridine is obtained；
The structure of the bromide containing pyridine is
(5) with the chloro- 4,6- diphenyl -1,3,5- triazine of 2- or 2,4- bis- ([1,1'- biphenyl] -4- base) chloro- 1,3,5- of -6-
Triazine and 3- bromobenzeneboronic acid carry out coupling reaction, and subsequent processing obtains brominated intermediate；
The structure of the brominated intermediate is
(6) brominated intermediate in step (5) is carried out Suzuki with connection boric acid pinacol rouge to react, subsequent processing obtains
Borate intermediate；
The structure of the borate intermediate is
(7) in catalyst system, the borate intermediate of the bromide and step (6) containing pyridine of step (4) is carried out
Coupling reaction, subsequent processing obtain soluble pyridine derivatives TRZ-Py-TPO (Formulas I) or the BPTRZ- of Asymmetrical substitute
Py-TPO (Formula II).
The condition of reaction described in step (1) is 8~16h of room temperature reaction；Phenyl-dihalide, n-BuLi and chlorinated diphenyl base
The molar ratio of phosphine is 1:(1.1~1.3): (1.3~1.5)；The reaction is using organic solvent as reaction medium；The organic solvent
Preferably tetrahydrofuran；
The specific steps of step (1): under protectiveness atmosphere, phenyl-dihalide is dissolved in organic solvent, is cooled to -70
~-78 DEG C, n-BuLi is added and is uniformly mixed, chloride 2-phenyl-phosphine is added.
Step (2) reaction condition is 10~12h of room temperature reaction, and the reaction is using organic solvent as reaction medium；Institute
Stating organic solvent is preferably methylene chloride；
The condition of reaction described in step (3) is 68~80 DEG C of 3~4h of reaction, the brominated intermediate product of oxidation and double valeryls
The molar ratio of two boron is 1:(1.3~1.5)；The palladium catalyst is bis- (triphenylphosphine) palladium chlorides；The oxidation it is brominated
The molar ratio of intermediate and palladium catalyst is 1:(0.01~0.03)；The reaction is using organic solvent as reaction medium；It is described to have
Solvent is preferably tetrahydrofuran；The system of the reaction further includes alkali compounds, and the alkali compounds is preferably acetic acid
Potassium.
In step (4) molar ratio of the intermediate product of boracic acid esters, 2,6- dibromo pyridine and palladium catalyst be 1:(1.0~
1.1): (0.01~0.03)；The palladium catalyst is tetrakis triphenylphosphine palladium；The system of the coupling reaction further includes alkaline water
Solution and consisting of phase-transferring agent, the alkaline aqueous solution are preferably aqueous sodium carbonate, and the consisting of phase-transferring agent is ethyl alcohol；In step (4)
The condition of the coupling reaction is 80~90 DEG C of 10~12h of reaction, and the reaction is described organic using organic solvent as reaction medium
Solvent is preferably toluene.
The chloro- 4,6- diphenyl -1,3,5- triazine of 2- or 2,4- bis- ([1,1'- biphenyl] -4- base) -6- chloro- 1 in step (5),
3,5- triazines and the molar ratio of 3- bromobenzeneboronic acid are 1:(1.0~1.1), the coupling reaction carries out in catalyst system, catalysis
System includes catalyst, and the catalyst is palladium catalyst, and the palladium catalyst is tetrakis triphenylphosphine palladium, the 3- bromobenzene boron
The molar ratio of acid and catalyst is (1.0~1.1): (0.01~0.03)；The catalyst system further includes alkaline aqueous solution and phase
Transfer agent, the alkaline aqueous solution are preferably aqueous sodium carbonate, and the consisting of phase-transferring agent is ethyl alcohol；It is coupled described in step (5)
The condition of reaction is 80~90 DEG C of 10~12h of reaction；Using organic solvent as reaction medium, the organic solvent is preferred for the reaction
For toluene.
The condition of reaction described in step (6) is 80~90 DEG C of 3~4h of reaction；The brominated intermediate and connection boric acid frequency which
The molar ratio of alcohol ester is 1:(1.1~1.5)；The reaction carries out in catalyst system, and catalyst system includes palladium catalyst, described
Palladium catalyst is bis- (triphenylphosphine) palladium chlorides；The molar ratio of the brominated intermediate and palladium catalyst be 1:(0.01~
0.03)；Using organic solvent as reaction medium, the organic solvent is tetrahydrofuran for the reaction；The catalyst system further includes
Alkali compounds, the alkali compounds are preferably potassium acetate.
Catalyst system described in step (7) includes catalyst, and the catalyst is palladium catalyst, and the palladium catalyst is four
(triphenylphosphine) palladium；The catalyst system further includes alkaline aqueous solution and consisting of phase-transferring agent, and the alkaline aqueous solution is that potassium carbonate is molten
Liquid or aqueous sodium carbonate, the consisting of phase-transferring agent are ethyl alcohol；Bromide and borate intermediate in step (7) containing pyridine rub
You are than being (1~1.2): 1；The condition of coupling reaction described in step (7) is 90~100 DEG C of reaction 10~16h, it is described react with
Organic solvent is reaction medium, and the organic solvent is preferably toluene.
Subsequent processing described in step (1) refers to that ethyl alcohol, which will after reaction, be added, terminates reaction, vacuum distillation, with water
Mixing, is extracted with dichloromethane, and will filter after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, uses column
Chromatography separation.
Subsequent processing described in step (2) is directed to that the excessive dioxygen of sodium sulfite aqueous solution reduction is added in reaction product
Water, and be extracted with dichloromethane, it will be filtered after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, uses column
Chromatography separation.
Subsequent processing described in step (3), which refers to, is evaporated under reduced pressure reaction product, mixes with water, is extracted with methylene chloride
It takes, will be filtered after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, is separated with column chromatography.
Subsequent processing described in step (4) is directed to that distilled water is added in reaction product, separates organic layer, uses methylene chloride
Aqueous layer extracted will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, uses column chromatography
Separation.
Subsequent processing described in step (5) is directed to that distilled water is added in reaction product, separates organic layer, uses methylene chloride
Aqueous layer extracted will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, uses column chromatography
Separation.
Subsequent processing described in step (6) refers to that reaction product is evaporated under reduced pressure by finger, is dissolved with methylene chloride, is added
Distilled water is simultaneously extracted with dichloromethane, and will filter after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, uses
Column chromatography separation.
Subsequent processing described in step (7) is directed to that distilled water is added in reaction product, separates organic layer, uses methylene chloride
Aqueous layer extracted will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, uses column chromatography
Separation.
A kind of Organic Electron Transport Material, in the soluble pyridine derivatives including above-mentioned Asymmetrical substitute one kind with
On, the soluble pyridine derivatives of more than one Asymmetrical substitutes in preferably above-mentioned Formulas I or Formula II.
The n- doping electron transfer layer is to carry out n- by the above-mentioned Organic Electron Transport Material of dopant to adulterate to obtain.
The dopant is preferably 8-hydroxyquinoline lithium-complex (Liq)；The doping of dopant meets the following conditions: mixing
The mass ratio of miscellaneous dose and Organic Electron Transport Material is (0.3~2): 1.
Application of the Organic Electron Transport Material in organic electroluminescence device, answering especially in phosphorescent devices
With.
Application of the n- doping electron transfer layer in organic electroluminescence device.
The principle of the present invention is as follows:
The present invention introduces 2,4,6- triphenyl -1,3,5- on diphenyl (3- (pyridine -2- base) phenyl) phosphine oxide group
TriazineOr 2,4- bis- ([1,1'- biphenyl] -4- base) -6- phenyl -1,3,5- triazineUnit has obtained small organic molecule electron transport material TRZ-Py-TPO and BPTRZ-Py-TPO.
2,4,6- cyanphenine 2,4,6 unit and 2,4- bis- ([1,1'- biphenyl] -4- base) -6- phenyl -1,3,5- 5-triazine units make
Obtain small organic molecule electron transport material mobility with higher；And aryl phosphine oxygen groups can improve compound and have common
Dissolubility (such as methylene chloride, chloroform, ethyl alcohol and ethyl acetate etc.) in solvent, is conducive to the purification of material.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) Organic Electron Transport Material of the invention has good thermal stability, the temperature of TRZ-Py-TPO weightlessness 1%
It is 370 DEG C, the temperature of the weightlessness 1% of BPTRZ-Py-TPO is 470 DEG C；The glass transition temperature of two compounds is respectively
102 DEG C and 123 DEG C；
(2) Organic Electron Transport Material of the invention have the characteristics that structure be synthetically prepared it is simple, and have it is good
Dissolubility, dissolubility such as in methylene chloride are greater than 100mg/ml, and dissolubility in ethanol is greater than 10mg/ml；
(3) Organic Electron Transport Material of the invention electron mobility with higher, TRZ-Py- after n- adulterates Liq
The electron mobility of TPO is 4.99 × 10-6-4.58×10-5cm2·V-1·s-1(@2-5×105V·cm-1), BPTRZ-Py-
TPO has higher electron mobility (4.66 × 10-5-3.21×10-4cm2·V-1·s-1@2-5×105V·cm-1), it is high
In the mobility (9.3 × 10 of Phen-NaDPO:Liq-7-6.6×10-6cm2·V-1·s-1@2-5×105V·cm-1；Patent
ZL201310275234.2, a kind of alcohol-soluble cathode buffer layer molecule profile containing triaryl phosphorus oxygen and azacyclo- functional group
Material and its synthetic method)；
(4) Organic Electron Transport Material of the invention is applied to obtain in green light phosphorescent devices after n- adulterates Liq higher
Device efficiency and stability: in 1000cdm-2Brightness under, the current efficiency and power efficiency of TRZ-Py-TPO device point
Not reaching 72.1cd/A, 75.5m/W, the current efficiency and power efficiency of BPTRZ-Py-TPO device are respectively 77.4cd/A,
86.8lm/W；It is 1000cdm in starting brightness under constant current driven-2Brightness under work after about 640h, brightness does not have substantially
There is decaying.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the Organic Electron Transport Material TRZ-Py-TPO of embodiment 1；
Fig. 2 is the thermal stability curve of the Organic Electron Transport Material TRZ-Py-TPO of embodiment 1；Wherein Fig. 2 a and Fig. 2 b
The respectively thermogravimetric curve and differential scanning calorimetric curve of the Organic Electron Transport Material TRZ-Py-TPO of embodiment 1；
Fig. 3 is the uv-visible absorption spectra of the Organic Electron Transport Material TRZ-Py-TPO of embodiment 1；
Fig. 4 is Organic Electron Transport Material TRZ-Py-TPO prepared by embodiment 1 and Liq 1:1n- in mass ratio doping
Electron mobility-electric field strength characteristic curve；
Fig. 5 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Current density-voltage-brightness curve of electroluminescent device；
Fig. 6 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Current efficiency-brightness curve (i.e. luminous efficiency-brightness curve) of electroluminescent device；
Fig. 7 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Power efficiency-brightness curve of electroluminescent device；
Fig. 8 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Brightness-time graph of electroluminescent device；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of the BPTRZ-Py-TPO of embodiment 2；
Figure 10 is the thermal stability curve of the small organic molecule electron transport material BPTRZ-Py-TPO of embodiment 2；Wherein
Figure 10 a and Figure 10 b are respectively the thermogravimetric curve and difference of the small organic molecule electron transport material BPTRZ-Py-TPO of embodiment 2
Show scanning calorimetric curve；
Figure 11 is the uv-visible absorption spectra of the Organic Electron Transport Material BPTRZ-Py-TPO of embodiment 2；
Figure 12 is that Organic Electron Transport Material BPTRZ-Py-TPO prepared by embodiment 2 and Liq 1:1n- in mass ratio is adulterated
Electron mobility-electric field strength characteristic curve；
Figure 13 is that the top emitting green light phosphorescence of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is had
Current density-voltage-brightness curve of organic electroluminescence devices；
Figure 14 is that the top emitting green light phosphorescence of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is had
Current efficiency-brightness curve (i.e. luminous efficiency-brightness curve) of organic electroluminescence devices；
Figure 15 is that the top emitting green light phosphorescence of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is had
Power efficiency-brightness curve of organic electroluminescence devices；
Figure 16 is that the top emitting green light phosphorescence of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is had
Brightness-time graph of organic electroluminescence devices.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
Embodiment 1
The structural formula of the Organic Electron Transport Material TRZ-Py-TPO of the present embodiment:
The preparation method of the Organic Electron Transport Material TRZ-Py-TPO of the present embodiment, comprising the following steps:
Step 1, the preparation of (3- bromophenyl) diphenylphosphine (1)
In N2Under atmosphere, 1,3- dibromobenzene (3.5g, 15.04mmol) is dissolved in dry tetrahydrofuran (200mL), it is cold
But -78 DEG C are arrived；Then, n-BuLi (2.5M hexane solution, 7.8mL, 19.55mmol) is added dropwise to by syringe；30 points
Clock afterchlorinate diphenylphosphine (4.1mL, 22.56mmol)) it is added by syringe；Mixed liquor, which is restored to, to be continued to stir at room temperature
12h；To the end of reacting, ethyl alcohol is added and terminates reaction, after solvent is removed under reduced pressure, reaction mixture is poured into water, and use dichloro
Methane extraction；Organic layer is dried, filtered with anhydrous magnesium sulfate, uses silica gel post separation after solvent is removed under reduced pressure, eluant, eluent is petroleum
The mixed solvent of ether and methylene chloride (4:1v/v) obtains white solid (3- bromophenyl) diphenylphosphine (1).
Step 2, the preparation of (3- bromophenyl) diphenyl phosphine oxide (2)
Into methylene chloride (20mL) solution of compound (1) (3- bromophenyl) diphenylphosphine (4.18g, 12.29mmol)
It is 30% hydrogen peroxide (6mL) that mass concentration, which is added, and 12h is stirred at room temperature；To the end of reacting, Asia is poured into reaction mixture
Aqueous sodium persulfate solution is extracted with dichloromethane with restoring excessive hydrogen peroxide；Organic layer is dried, filtered with anhydrous magnesium sulfate,
Silica gel post separation is used after solvent is removed under reduced pressure, eluant, eluent is methylene chloride, obtains the oxidation of white solid (3- bromophenyl) diphenyl
Phosphine (2), yield 96% (4.2g).
Step 3, diphenyl (3- (4,4,5,5- tetramethyls -1,3,2-2- dioxaborinate base) phenyl) phosphine oxide (3)
Preparation
In N2Under atmosphere, will be bis- (triphenylphosphine) palladium chloride (80mg, 0.11mmol) be added to compound (2) (3- bromine
Phenyl) diphenyl phosphine oxide (2.3g, 6.44mmol), bis (pinacolato) diboron (2.45g, 9.66mmol) and potassium acetate (1.9g,
In tetrahydrofuran (60mL) mixed liquor 19.32mmol), heating reflux reaction 3 hours；It is to be cooled to arrive room temperature, it is removed under reduced pressure molten
After agent, reaction mixture is poured into water, and is extracted with dichloromethane；Organic layer is dried, filtered with anhydrous magnesium sulfate, and decompression removes
Silica gel post separation is used after removing solvent, eluant, eluent is the mixed solvent of methylene chloride and ethyl acetate (4:1v/v), and it is solid to obtain white
Body diphenyl (3- (4,4,5,5- tetramethyls -1,3,2-2- dioxaborinate base) phenyl) phosphine oxide (compound 3), yield 94%
(2.44g)。
Step 4, the preparation of (3- (6- bromopyridine -2- base) phenyl) diphenyl phosphine oxide (4)
In N2Under atmosphere, tetrakis triphenylphosphine palladium (70mg) is added to compound (3) (2.44g, 6.03mmol), 2,6-
Toluene (100ml) mixed liquor of dibromo pyridine (1.43g, 6.03mmol), ethyl alcohol (8ml) and aqueous sodium carbonate (2M, 8ml)
In, it is stirred to react at 90 DEG C 12 hours；To after reaction, distilled water separation of methylbenzene layer be added to reaction mixture, with two
Chloromethanes aqueous layer extracted will filter after organic layer extracted anhydrous magnesium sulfate drying, and vacuum distillation removes methylene chloride, obtains
To crude product separated with column chromatography, eluant, eluent be methylene chloride and ethyl acetate (3:1v/v) mixed solvent, obtain white
Color solid (compound 4), yield 80% (2.1g).
Step 5,2- (3- bromophenyl) -4,6- diphenyl -1,3,5-triazines (5) preparation
In N2Under atmosphere, tetrakis triphenylphosphine palladium (110mg) is added to chloro- 4, the 6- diphenyl -1,3,5-triazines of 2-
(4.0g, 14.94mmol), the bromo- phenyl boric acid of 3- (3.0g, 14.94mmol), ethyl alcohol (15ml) and aqueous sodium carbonate (2M,
In toluene (100ml) mixed liquor 15ml), it is stirred to react at 90 DEG C 12 hours；To after reaction, to reaction mixture plus
Enter distilled water separation of methylbenzene layer, water layer be extracted with dichloromethane, will be filtered after organic layer extracted anhydrous magnesium sulfate drying,
Vacuum distillation removes methylene chloride, and obtained crude product is separated with column chromatography, and eluant, eluent is petroleum ether, obtains white solid
(compound 5), yield 77.6% (4.5g).
Step 6,2,4- diphenyl -6- (3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolane -2- base) benzene
Base) -1,3,5- triazine (6) preparation
In N2Under atmosphere, will be bis- (triphenylphosphine) palladium chloride (80mg, 0.11mmol) be added to compound 5 (4.5g,
11.59mmol), join the tetrahydrofuran of boric acid pinacol rouge (4.3g, 17.38mmol), potassium acetate (3.41g, 34.77mmol)
In (100ml) mixed liquor, it is stirred to react at 80 DEG C 3 hours；To which after reaction, vacuum distillation removes tetrahydrofuran, with two
Chloromethanes dissolution is added distilled water and is extracted with dichloromethane, and filters, depressurizes after the anhydrous magnesium sulfate drying of obtained organic layer
Methylene chloride is distilled off, obtained crude product is separated with column chromatography, and eluant, eluent is petroleum ether and methylene chloride (2:1v/v)
Mixed solvent, obtain white solid (compound 6), yield 93% (4.7g).
Step 7, (3- (6- (3- (6,6- diphenyl -1,3,5-triazines -2- base) phenyl) pyridine -2- base) phenyl) diphenyl
The preparation of phosphine oxide (TRZ-Py-TPO)
In N2Under atmosphere, tetrakis triphenylphosphine palladium (110mg) is added to compound 4 (2.99g, 6.89mmol), chemical combination
In toluene (50ml) mixed liquor of object 6 (3.0g, 6.89mmol), ethyl alcohol (7ml) and wet chemical (2M, 7ml), at 90 DEG C
Under be stirred to react 16 hours；To after reaction, distilled water separation of methylbenzene layer be added to reaction mixture, is extracted with dichloromethane
Water layer will filter after organic layer extracted anhydrous magnesium sulfate drying, and vacuum distillation removes methylene chloride, obtained crude product
It is separated with column chromatography, eluant, eluent is the mixed solvent of methylene chloride and ethyl acetate (4:1v/v), obtains white solid (TRZ-
Py-TPO), yield 61% (2.8g).
Structural characterization and performance are carried out to small organic molecule electron transport material TRZ-Py-TPO prepared by embodiment 1 below
Test:
(1) nuclear magnetic resonance spectroscopy
1H NMR(400MHz,CDCl3) δ 9.43 (s, 1H), 8.83 (ddd, J=12.8,8.0,1.5Hz, 5H), 8.54
(dd, J=7.7,1.3Hz, 1H), 8.47 (d, J=12.7Hz, 1H), 8.38 (dd, J=7.7,1.1Hz, 1H), 7.96-7.86
(m,2H),7.80–7.68(m,7H),7.67–7.53(m,9H),7.53–7.43(m,4H).
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the Organic Electron Transport Material TRZ-Py-TPO of embodiment 1.
(2) macroscopic property
Thermogravimetic analysis (TGA) (TGA) is to lead to nitrogen protection on TGA2050 (TA instruments) thermogravimetric analyzer with 20
DEG C/determination of heating rate of min；Differential scanning calorimetric analysis (DSC) uses NETZSCH DSC204F1 thermal analyzer, in nitrogen
In gas atmosphere, with the heating rate of 10 DEG C/min to 350 DEG C since -30 DEG C, -30 DEG C then are cooled to 20 DEG C/min, perseverance
Warm 5min is tested with the heating rate of 10 DEG C/min to 350 DEG C again.Test results are shown in figure 2.Fig. 2 is having for embodiment 1
The thermal stability curve of machine electron transport material TRZ-Py-TPO；Wherein Fig. 2 a and Fig. 2 b is respectively the organic electronic of embodiment 1
The thermogravimetric curve and differential scanning calorimetric curve of transmission material TRZ-Py-TPO.
Show that temperature when TRZ-Py-TPO weightlessness 1% is 370 DEG C by Fig. 2 a thermogravimetric curve, heat with higher is steady
It is qualitative.
Show to heat in the first round by Fig. 2 b differential scanning calorimetric curve, compound TRZ-Py-TPO occurs significantly
Melting peak, corresponding fusing point are 214 DEG C.The small organic molecule electron transport material in first round cooling and the second wheel temperature-rise period
There is peak crystallization and melting peak not in TRZ-Py-TPO, but apparent glass transition occurs at 102 DEG C.
(3) Photophysics
The uv-visible absorption spectra that Fig. 3 is Organic Electron Transport Material TRZ-Py-TPO prepared by embodiment 1 (shines
The corresponding transmitting of intensity-wavelength, absorbance-wavelength is corresponding to be absorbed).From the absorption spectrum in Fig. 3, light can determine according to ABSORPTION EDGE
Band gap is 3.63eV.
(4) electron mobility
Single-electron device (ITO/TRZ-Py-TPO:Liq (50%wt, 150nm)/Al) is prepared, according to Current density-voltage
Curve calculates electron mobility by space charge limited current SCLC method.Liq is 8-hydroxyquinoline lithium-complex.50%wt
The mass ratio for indicating Liq and TRZ-Py-TPO is 1:1.
Single-electron device detailed preparation process is as follows:
It is 10-20 Ω/mouth tin indium oxide (ITO) electro-conductive glass substrate successively through deionized water, acetone, washing by resistance
Agent, deionized water and isopropanol are cleaned by ultrasonic 20min respectively.After oven drying, above-mentioned processed ito glass substrate is existed
3×10-4Under the vacuum of Pa, each organic function layer and metal Al cathode is deposited.Film thickness Veeco Dektak150 step
Instrument measurement.The deposition rate and its thickness of metal electrode vapor deposition are surveyed with thickness/speed instrument STM -100 of Sycon Instrument
It is fixed.Fig. 4 is that the electronics of Organic Electron Transport Material TRZ-Py-TPO and Liq 1:1n- in mass ratio doping prepared by embodiment 1 moves
Shifting rate-electric field strength profile.
As shown in figure 4, being calculated according to SCLC, the small organic molecule electron transport material TRZ-Py-TPO of the present embodiment
Electron mobility be 4.99 × 10-6-4.58×10-5cm2·V-1·s-1(@2-5×105V·cm-1)。
(5) the electron-transport material layer as n- doping, using the characterization of the organic electroluminescence device of vacuum vapour deposition
The small organic molecule electron transport material TRZ-Py-TPO n- doping Liq prepared using embodiment 1 is passed as electronics
Defeated layer, prepares device architecture: Ag/ITO/P008:F4-TCNQ (147nm, 4%)/NPB (15nm)/EBL-1 (5nm)/HOST-
09:HOST-08:GD-L1 (30nm, 0.5:0.5:15%)/TRZ-Py-TPO:Liq (30nm, 1:1)/Mg:Ag (15nm, 1:9)/
CP501(70nm).Other organic materials used can be commercialized direct purchase in addition to Organic Electron Transport Material.Wherein,
P008:F4-TCNQ is as hole injection layer (Beijing Ding Cai Science and Technology Ltd.), and NPB is as hole transmission layer, Host09:
Host08:GD-L1 is as luminescent layer (GD-L1 is green light phosphorescent complexes, material based on Host09/Host08) (GD-L1 purchase
Taiwan sunlight radium is purchased from from Taiwan machine Micron Technology Co., Ltd Luminescence Technology Crop., Host09/Host08
Photoelectric material Co., Ltd), CP501 is as light removing layer (being purchased from Beijing Ding Cai Science and Technology Ltd.), TRZ-Py-TPO:Liq
As electron transfer layer.P008:4wt%F4-TCNQ (being purchased from Beijing Ding Cai Science and Technology Ltd.) Thin film conductive rate is about 2.65
×10-4S m-1。
Device detailed preparation process is as follows:
It is 10-20 Ω/mouth tin indium oxide (ITO) electro-conductive glass substrate successively through deionized water, acetone, washing by resistance
Agent, deionized water and isopropanol are cleaned by ultrasonic 20min respectively.After oven drying, above-mentioned processed ito glass substrate is existed
3×10-4Under the vacuum of Pa, each organic function layer and metal Al cathode is deposited.Film thickness Veeco Dektak150 step
Instrument measurement.The deposition rate and its thickness of metal electrode vapor deposition are surveyed with thickness/speed instrument STM -100 of Sycon Instrument
It is fixed.The performance test results of organic electroluminescence device are as shown in figures 5-8.
Fig. 5 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Current density-voltage-brightness curve of electroluminescent device；Fig. 6 is the Organic Electron Transport Material prepared using embodiment 1
Current efficiency-brightness curve of the top emitting green light phosphorescent organic electroluminescent device of TRZ-Py-TPO；Fig. 7 is using embodiment
The power efficiency-of the top emitting green light phosphorescent organic electroluminescent device of the Organic Electron Transport Material TRZ-Py-TPO of 1 preparation
Brightness curve；Fig. 8 is that the top emitting green light phosphorescence of the Organic Electron Transport Material TRZ-Py-TPO prepared using embodiment 1 is organic
Brightness-time graph of electroluminescent device.
As illustrated in figs. 5-7, the organic electroluminescence device made with vacuum deposition method, using electron transport material TRZ-
After Py-TPO n- adulterates Liq as electron transfer layer, in 1000cdm-2Brightness under, the current efficiency and function of green light phosphorescence
Rate efficiency has respectively reached 72.1cd/A, 75.5m/W.
Preliminary device stability, which is tested, to be shown (such as Fig. 8), the top emitting green light phosphorescent devices of TRZ-Py-TPO preparation, in perseverance
Under electric current driving, in starting brightness 1000cdm-2Brightness does not decay substantially after lower work about 640 hours.
The above results show that above-mentioned doping type electron transport material TRZ-Py-TPO can get high-luminous-efficiency and high stable
Property.
Embodiment 2
The structural formula of the organic molecule electron transport material BPTRZ-Py-TPO of the present embodiment is as follows:
The preparation method of the organic molecule electron transport material BPTRZ-Py-TPO of the present embodiment, comprising the following steps:
Step 1-4 is same as Example 1.
Step 5, the preparation of 2,4- bis- ([1,1'- biphenyl] -4- base) -6- (3- bromophenyl) -1,3,5-triazines (5)
Operating method is similar to embodiment 1, and details are not described herein, and yield is 78% (5.0g).
Step 6,2,4- bis- ([1,1'- biphenyl] -4- base) -6- (3- (4,4,5,5- tetramethyls -1,3,2- dioxo bora ring
Pentane -2- base) phenyl) -1,3,5- triazine (6) preparation
Operating method is similar to embodiment 1, and details are not described herein, and yield is 81.5% (4.4g).
Step 7, (3- (6- (3- (4,6- bis- ([1,1'- biphenyl] -4- base) -1,3,5-triazines -2- base) phenyl) pyridine -2-
Base) phenyl) diphenyl phosphine oxide (BPTRZ-Py-TPO) preparation
Operating method is similar to embodiment 1, and details are not described herein, yield 77% (3.2g).
Structural characterization and property are carried out to small organic molecule electron transport material BPTRZ-Py-TPO prepared by embodiment 2 below
It can test:
(1) nuclear magnetic resonance spectroscopy
1H NMR(400MHz,CDCl3) δ 9.43 (s, 1H), 8.87 (m, J=8.1,6.4Hz, 5H), 8.51 (m, J=
21.3,10.2Hz, 2H), 8.40 (d, J=7.9Hz, 1H), 7.92 (m, J=7.8Hz, 2H), 7.82 (d, J=8.5Hz, 4H),
7.79-7.69 (m, 11H), 7.66 (td, J=7.6,3.2Hz, 1H), 7.57 (m, J=7.3,1.4Hz, 2H), 7.54-7.46
(m,8H),7.46–7.39(m,2H).
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of the Organic Electron Transport Material BPTRZ-Py-TPO of embodiment 2.
(2) macroscopic property
Thermogravimetic analysis (TGA) (TGA) is to lead to nitrogen protection on TGA2050 (TA instruments) thermogravimetric analyzer with 20
DEG C/determination of heating rate of min；Differential scanning calorimetric analysis (DSC) uses 204 F1 thermal analyzer of NETZSCH DSC,
In nitrogen atmosphere, with the heating rate of 10 DEG C/min to 450 DEG C since -30 DEG C, -30 DEG C then are cooled to 20 DEG C/min,
Constant temperature 5min is tested with the heating rate of 10 DEG C/min to 450 DEG C again.Test results are shown in figure 10.Figure 10 is embodiment 2
Organic Electron Transport Material BPTRZ-Py-TPO thermal stability curve；Wherein Figure 10 a and Figure 10 b is respectively embodiment 2
The thermogravimetric curve and differential scanning calorimetric curve of Organic Electron Transport Material BPTRZ-Py-TPO.
Show that temperature when BPTRZ-Py-TPO weightlessness 1% is 470 DEG C by Figure 10 a thermogravimetric curve, heat with higher
Stability.
Show to heat in the first round by Figure 10 b differential scanning calorimetric curve, compound BPTRZ-Py-TPO occurs obviously
Melting peak, corresponding fusing point be 262 DEG C.The small organic molecule electron transport material BPTRZ-Py- in the second wheel heating process
There is apparent peak crystallization and melting peak in TPO, and crystallization temperature is 209 DEG C, and fusing point is 261 DEG C.Furthermore BPTRZ-Py-TPO table
Reveal apparent glass transition, corresponding glass transition temperature is 123 DEG C.
(3) Photophysics
Figure 11 is the uv-visible absorption spectra of Organic Electron Transport Material BPTRZ-Py-TPO prepared by embodiment 2.From
In absorption spectrum in Figure 11, it can determine that optical band gap is 3.38eV according to ABSORPTION EDGE.
(4) electron mobility
Figure 12 is that Organic Electron Transport Material BPTRZ-Py-TPO prepared by embodiment 2 and Liq 1:1n- in mass ratio is adulterated
Electron mobility-electric field strength profile.
As shown in figure 12, it is calculated according to SCLC, the Organic Electron Transport Material BPTR Z-Py-TPO's of the present embodiment
Electron mobility is 4.66 × 10-5-3.21×10-4cm2·V-1·s-1(@2-5×105V·cm1)。
(5) the electron-transport material layer as n- doping, using the characterization of the organic electroluminescence device of vacuum vapour deposition
The small organic molecule electron transport material BPTRZ-Py-TPO n- doping Liq prepared using embodiment 2 is as electronics
Transport layer prepares device architecture: Ag/ITO/P008:F4-TCNQ (147nm, 4%)/NPB (15n m)/EBL-1 (5nm)/
HOST-09:HOST-08:GD-L1 (30nm, 0.5:0.5:15%)/BPTRZ-Py-TPO:Liq (30nm, 1:1)/Mg:Ag
(15nm,1:9)/CP501(70nm)。
The preparation process of device is same as Example 1, the performance test results of organic electroluminescence device such as Figure 13~16
It is shown.
Figure 13 is that the top emitting green light phosphorescence of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is had
Current density-voltage-brightness curve of organic electroluminescence devices；Figure 14 is that the organic electronic prepared using embodiment 2 transmits material
Expect current efficiency-brightness curve of the top emitting green light phosphorescent organic electroluminescent device of BPTRZ-Py-TPO；Figure 15 is to use
The function of the top emitting green light phosphorescent organic electroluminescent device of Organic Electron Transport Material BPTRZ-Py-TPO prepared by embodiment 2
Rate ciency-luminance curve；Figure 16 is that the top emitting of the Organic Electron Transport Material BPTRZ-Py-TPO prepared using embodiment 2 is green
Brightness-time graph of light phosphorescent organic electroluminescent device
As illustrated in figs. 13-15, the organic electroluminescence device made with vacuum deposition method, using electron transport material
After BPTRZ-Py-TPO n- adulterates Liq as electron transfer layer, in 1000cdm-2Brightness under, the electric current of green light phosphorescence is imitated
Rate and power efficiency have respectively reached 77.4cd/A, 86.8lm/W.
As shown in figure 16, the top emitting green light phosphorescent devices of BPTRZ-Py-TPO preparation are originating under constant current driving
Brightness 1000cdm-2Brightness does not decay substantially after lower work about 640 hours.
The above results show that above-mentioned doping type electron transport material BPTRZ-Py-TPO can get high-luminous-efficiency and height is steady
It is qualitative.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of soluble pyridine derivatives of Asymmetrical substitute, it is characterised in that: for one kind in following formula I or Formula II with
It is upper:
2. the preparation method of the soluble pyridine derivatives of Asymmetrical substitute according to claim 1, it is characterised in that: packet
Include following steps:
(1) under the action of n-BuLi, diphenyl phosphine chloride is reacted, subsequent processing with phenyl-dihalide, is obtained unoxidized
Brominated intermediate product；The phenyl-dihalide is m-dibromobenzene, diiodo-benzene or the bromo- 3- iodobenzene of 1-；
The structure of the unoxidized brominated intermediate product is
(2) hydrogen peroxide oxidation processing step (1) resulting unoxidized brominated intermediate product is used, subsequent processing is aoxidized
Brominated intermediate product；
The structural formula of the brominated intermediate product of the oxidation is
(3) under the action of palladium catalyst, the brominated intermediate product of step (2) resulting oxidation is reacted with bis (pinacolato) diboron,
Obtain the intermediate product containing borate；
The structure of the intermediate product containing borate is
(4) by the effect of palladium catalyst, by the intermediate product and 2 of the resulting boracic acid esters of step (3), 6- dibromo pyridine is carried out
Coupling reaction obtains the bromide containing pyridine；
The structure of the bromide containing pyridine is
(5) with the chloro- 4,6- diphenyl -1,3,5- triazine of 2- or 2,4- bis- ([1,1'- biphenyl] -4- base) chloro- 1,3,5- triazine of -6-
Coupling reaction is carried out with 3- bromobenzeneboronic acid, subsequent processing obtains brominated intermediate；
The structure of the brominated intermediate is
(6) brominated intermediate in step (5) is carried out Suzuki with connection boric acid pinacol rouge to react, subsequent processing obtains boric acid
Ester intermediate；
The structure of the borate intermediate is
(7) in catalyst system, the borate intermediate of the bromide containing pyridine of step (4) and step (6) is coupled
Reaction, subsequent processing, the soluble pyridine derivatives for obtaining Asymmetrical substitute are denoted as TRZ-Py-TPO, structure be Formulas I or
It is denoted as BPTRZ-Py-TPO, structure is Formula II；
3. the preparation method of the soluble pyridine derivatives of Asymmetrical substitute according to claim 2, it is characterised in that: step
Suddenly the condition of reaction described in (1) is 8~16h of room temperature reaction；The molar ratio of phenyl-dihalide, n-BuLi and chloride 2-phenyl-phosphine
For 1:(1.1~1.3): (1.3~1.5)；The reaction is using organic solvent as reaction medium；
Step (2) reaction condition is 10~12h of room temperature reaction, and the reaction is using organic solvent as reaction medium；
The condition of reaction described in step (3) is 68~80 DEG C of 3~4h of reaction, the brominated intermediate product and bis (pinacolato) diboron of oxidation
Molar ratio be 1:(1.3~1.5)；The palladium catalyst is bis- (triphenylphosphine) palladium chlorides；The brominated centre of the oxidation
The molar ratio of body and palladium catalyst is 1:(0.01~0.03)；The reaction is using organic solvent as reaction medium；The reaction
System further includes alkali compounds；
The molar ratio of the intermediate product of boracic acid esters, 2,6- dibromo pyridine and palladium catalyst is 1:(1.0~1.1 in step (4)):
(0.01~0.03)；The palladium catalyst is tetrakis triphenylphosphine palladium；The system of the coupling reaction further includes alkaline aqueous solution
And consisting of phase-transferring agent；The condition of coupling reaction described in step (4) is 80~90 DEG C of 10~12h of reaction, and the reaction is with organic molten
Agent is reaction medium；
The chloro- 4,6- diphenyl -1,3,5- triazine of 2- or 2,4- bis- ([1,1'- biphenyl] -4- base) chloro- 1,3,5- of -6- in step (5)
Triazine and the molar ratio of 3- bromobenzeneboronic acid are 1:(1.0~1.1), the coupling reaction carries out in catalyst system, catalyst system
Including catalyst, the catalyst be palladium catalyst, the palladium catalyst be tetrakis triphenylphosphine palladium, the 3- bromobenzeneboronic acid with
The molar ratio of catalyst is (1.0~1.1): (0.01~0.03)；The catalyst system further includes alkaline aqueous solution and phase transfer
Agent；The condition of coupling reaction described in step (5) is 80~90 DEG C of 10~12h of reaction；The reaction is reaction with organic solvent
Medium；
The condition of reaction described in step (6) is 80~90 DEG C of 3~4h of reaction；The brominated intermediate and connection boric acid pinacol rouge
Molar ratio be 1:(1.1~1.5)；The reaction carries out in catalyst system, and catalyst system includes palladium catalyst, and the palladium is urged
Agent is bis- (triphenylphosphine) palladium chlorides；The molar ratio of the brominated intermediate and palladium catalyst is 1:(0.01~0.03)；
The reaction is using organic solvent as reaction medium；The catalyst system further includes alkali compounds；
Catalyst system described in step (7) includes catalyst, and the catalyst is palladium catalyst, and the palladium catalyst is four (three
Phenylphosphine) palladium；The catalyst system further includes alkaline aqueous solution and consisting of phase-transferring agent, bromide and boron containing pyridine in step (7)
The molar ratio of acid esters intermediate is (1~1.2): 1；The condition of coupling reaction described in step (7) be 90~100 DEG C reaction 10~
16h, the reaction is using organic solvent as reaction medium.
4. the preparation method of the soluble pyridine derivatives of Asymmetrical substitute according to claim 3, it is characterised in that: step
Suddenly alkali compounds described in (3) is potassium acetate；
Alkaline aqueous solution described in step (4) is aqueous sodium carbonate, and the consisting of phase-transferring agent is ethyl alcohol；
Alkaline aqueous solution described in step (5) is aqueous sodium carbonate, and the consisting of phase-transferring agent is ethyl alcohol；
Alkali compounds described in step (6) is potassium acetate；
Alkaline aqueous solution described in step (7) is solution of potassium carbonate or aqueous sodium carbonate, and the consisting of phase-transferring agent is ethyl alcohol.
5. the preparation method of the soluble pyridine derivatives of Asymmetrical substitute according to claim 2, it is characterised in that: step
Suddenly subsequent processing described in (1) refers to that ethyl alcohol, which will after reaction, be added, terminates reaction, and vacuum distillation mixes with water, uses dichloro
Methane extraction will filter after organic layer anhydrous magnesium sulfate drying, and vacuum distillation removes methylene chloride, is separated with column chromatography；
Subsequent processing described in step (2) is directed to that the excessive hydrogen peroxide of sodium sulfite aqueous solution reduction is added in reaction product,
And be extracted with dichloromethane, it will be filtered after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, is chromatographed with column
Method separation；
Subsequent processing described in step (3), which refers to, is evaporated under reduced pressure reaction product, mixes, is extracted with dichloromethane with water,
It will be filtered after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, is separated with column chromatography；
Subsequent processing described in step (4) is directed to that distilled water is added in reaction product, separates organic layer, is extracted with dichloromethane
Water layer will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, with column chromatography point
From；
Subsequent processing described in step (5) is directed to that distilled water is added in reaction product, separates organic layer, is extracted with dichloromethane
Water layer will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, with column chromatography point
From；
Subsequent processing described in step (6) refers to that reaction product is evaporated under reduced pressure by finger, is dissolved with methylene chloride, and distillation is added
Water is simultaneously extracted with dichloromethane, and will filter after organic layer anhydrous magnesium sulfate drying, vacuum distillation removes methylene chloride, with column layer
The separation of analysis method；
Subsequent processing described in step (7) is directed to that distilled water is added in reaction product, separates organic layer, is extracted with dichloromethane
Water layer will filter after the anhydrous magnesium sulfate drying of organic layer after extraction, and vacuum distillation removes methylene chloride, with column chromatography point
From.
6. a kind of Organic Electron Transport Material, it is characterised in that: the solubility including Asymmetrical substitute defined in claim 1
More than one in pyridine derivatives.
7. application of the Organic Electron Transport Material in organic electroluminescence device according to claim 6.
8. a kind of n- adulterates electron transfer layer, it is characterised in that: be to carry out n- to Organic Electron Transport Material by dopant to mix
Miscellaneous to obtain, the Organic Electron Transport Material is as defined in claim 6.
9. n- adulterates electron transfer layer according to claim 8, it is characterised in that: the dopant is that 8-hydroxyquinoline lithium is matched
Close object.
10. n- adulterates application of the electron transfer layer in organic electroluminescence device according to claim 8 or claim 9.
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| CN103087103A (en) * | 2013-01-28 | 2013-05-08 | 苏州纳凯科技有限公司 | Organic semiconductor material for organic electroluminescence device as well as preparation method and application thereof |
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| CN111205323A (en) * | 2020-01-17 | 2020-05-29 | 华南理工大学 | Asymmetric substituted anthracene-based derivative and preparation and application thereof |
| CN113013345A (en) * | 2021-02-25 | 2021-06-22 | 华南理工大学 | Application of low-refractive-index organic electron transmission material in top-emission organic light-emitting diode device |
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| CN110016053B (en) | 2020-08-18 |
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