CN106946860A - It is a kind of using triazine and benzimidazole as the organic compound of core and its application - Google Patents
It is a kind of using triazine and benzimidazole as the organic compound of core and its application Download PDFInfo
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- 0 CC1C(C)(CCC2)C2C2C3*4C1C4C2C3 Chemical compound CC1C(C)(CCC2)C2C2C3*4C1C4C2C3 0.000 description 11
- VZUFJZYIHPVGCC-UHFFFAOYSA-N BrC(C=C1)=CCC1N(c1ccccc1)c1cccc-2c1C(C1)C1c1ccccc-21 Chemical compound BrC(C=C1)=CCC1N(c1ccccc1)c1cccc-2c1C(C1)C1c1ccccc-21 VZUFJZYIHPVGCC-UHFFFAOYSA-N 0.000 description 1
- DZZWCNFALLLVTJ-UHFFFAOYSA-N CC(C)/N=C(\N=C(/NC)\Cl)/Cl Chemical compound CC(C)/N=C(\N=C(/NC)\Cl)/Cl DZZWCNFALLLVTJ-UHFFFAOYSA-N 0.000 description 1
- WSYJWNFHOYRCFD-UHFFFAOYSA-N CC1(C)OB(c(cc2)ccc2-[n]2c(-c3cnccc3)nc3c2cccc3)OC1(C)C Chemical compound CC1(C)OB(c(cc2)ccc2-[n]2c(-c3cnccc3)nc3c2cccc3)OC1(C)C WSYJWNFHOYRCFD-UHFFFAOYSA-N 0.000 description 1
- AHCUFSSSQHWMBZ-UHFFFAOYSA-N CC1(C)ON(c(cc2)ccc2N(c2ccccc2)c2ccccc2)OC1(C)C Chemical compound CC1(C)ON(c(cc2)ccc2N(c2ccccc2)c2ccccc2)OC1(C)C AHCUFSSSQHWMBZ-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N CCc1ccccc1 Chemical compound CCc1ccccc1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of using triazine and benzimidazole as the organic compound of core and its application in OLED, the compounds of this invention has higher glass transition temperature and molecule heat endurance;It is high in the low, refractive index of visible regime absorption, after applied to the CPL of OLED layers, it can effectively lift the light extraction efficiency of OLED;The compounds of this invention also has deep HOMO energy levels and high electron mobility, can as OLED hole barrier/electron transport layer materials, it can effectively stop that hole or energy are transferred to electronic shell side from luminescent layer, so as to lift the combined efficiency of hole and electronics in luminescent layer, and then lift the luminous efficiency and service life of OLED.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of organising as core using triazine and benzimidazole
Compound and its application on OLED.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used to make
New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is quite varied.OLED luminescent devices are just as the structure of sandwich, including electrode material film layer and are clipped in different electricity
Organic functional material between the film layer of pole, various difference in functionality materials is overlapped mutually according to purposes collectively constitute together OLED hairs
Optical device.OLED luminescent devices are as current device, when applying voltage to its two end electrodes, and pass through electric field action organic layer work(
Can be in film layer positive and negative charge when, positive and negative charge is further combined in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are in smart mobile phone, and the field such as panel computer is applied, further will also be to electricity
Depending on etc. large scale application field extension.But, due to there is huge spread between OLED external quantum efficiency and internal quantum efficiency,
Greatly constrain OLED development.Therefore, how to improve OLED light extraction efficiency turns into study hotspot.Ito thin film and glass
The interface of the interface of glass substrate and glass substrate and air can be totally reflected, and be shone before OLED to exterior space
Light account for the 20% of organic material film EL total amounts, remaining about 80% light is main, and in guided wave form to be limited in organic material thin
In film, ito thin film and glass substrate.It can be seen that the light extraction efficiency of conventional OLED device is relatively low (about 20%), this is seriously constrained
OLED development and application.How to reduce total reflection effect in OLED, improve optically coupling to before device to exterior space
Ratio (light extraction efficiency) cause the extensive concern of people.
At present, realize improve OLED external quantum efficiencys a class important method be substrate light output surface formation as fold,
The structures such as photonic crystal, lenticule display (MLA) and addition surface coating.First two structure can influence OLED radiation spectrum
Angular distribution, the third structure fabrication processes are complicated, and use surface coating technique simple, luminous efficiency improve 30% with
On, particularly people pay close attention to.According to optical principle, when light transmission superrefraction rate is n1Material to refractive index be n2Material when (n1
> n2), only in arcsin (n2/n1) angle in can just incide refractive index for n2Material in, absorptivity B can be used to
Under formula calculate:
If n1=nGeneral OLED organic materials=1.70, n2=nGlass=1.46, then 2B=0.49.Assuming that the whole quilts of the light outwards propagated
Metal electrode reflects, then only 51% luminous energy is by the organic film of high index of refraction and the waveguide of ITO layer institute, can equally calculate light from
Substrate of glass injects to transmitance during air.When therefore projecting the outside of device from the light that organic layer is sent, only about 17%
Luminous energy seen by people.Therefore, for the low present situation of current OLED light extraction efficiency, it is necessary to increase in the device structure
Plus one layer CPL layers, i.e. light extraction material, according to optical absorption, refraction principle, the refractive index of this surface coating material should be got over
It is high better.
Proposing high performance research to OLED luminescent devices at present includes:Reduce the driving voltage of device, improve the hair of device
Light efficiency, the service life for improving device etc..For the continuous lifting of the performance of realizing OLED, not only need from OLED devices
The innovation of part structure and manufacture craft, with greater need for the constantly research and innovation of oled light sulfate ferroelectric functional material, formulates out higher performance
OLED functional materials.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of using triazine and benzimidazole as core
Organic compound and its application on organic electroluminescence device.The compounds of this invention contains triazine and benzimidazole structure,
It is high in the low, refractive index of visible regime absorption with higher glass transition temperature and molecule heat endurance, applied to OLED devices
After the CPL layers of part, the light extraction efficiency of OLED can be effectively lifted;And because triazine and benzimidazole have deep HOMO
Energy level, wide forbidden band (Eg) energy level, can as OLED hole barrier/electron transport layer materials, stop hole from luminous
Layer is transferred to electronic shell side, the multiplicity of hole and electronics in luminescent layer is improved, so as to lift the luminous effect of OLED
Rate and service life.
Technical scheme is as follows:
The applicant provide it is a kind of using triazine and benzimidazole as the organic compound of core, the organic compound
Shown in structure such as formula (1):
In formula (1), Ar1、Ar2、Ar3Independently be expressed as C1-10Straight or branched alkyl;Halogen atom, protium,
Deuterium, the substituted or unsubstituted phenyl of tritium atom;Naphthyl;Dibiphenylyl;Terphenyl;Anthryl;Or one kind in pyridine radicals;Ar1、
Ar2、Ar3Can also be independently be expressed as singly-bound;
Ar1、Ar2、Ar3Can be with identical or different;
In formula (1), R1It is expressed as structure shown in formula (2);
In formula (2), R4、R5Independently be expressed as C1-10Straight or branched alkyl;Halogen atom, protium, deuterium, tritium are former
The substituted or unsubstituted phenyl of son;Naphthyl;Dibiphenylyl;Terphenyl;Anthryl;Pyridine radicals;Dibenzofurans;Dibenzo thiophene
Fen;9,9- dimethyl fluorenes;Or one kind in N- phenyl carbazoles;
R4、R5Can be with identical or different;
In formula (1), R2、R3Independently be expressed as formula (3), formula (4) or structure shown in formula (5);
Wherein, Ar4、Ar5、Ar6、Ar7Independently be expressed as C1-10Straight or branched alkyl;Halogen atom replace or not
Substituted phenyl;Naphthyl;Dibiphenylyl;Terphenyl;Or one kind in pyridine radicals;
R2、R3Can be with identical or different.
It is preferred that, the concrete structure formula of the organic compound is:
In any one.
The applicant additionally provides the reaction side occurred in a kind of preparation method of described organic compound, preparation process
Formula is:
Work as Ar1During for singly-bound,
Specifically course of reaction is:
Weigh the chloro- 1,3,5- triazines of raw material 2,4,6- tri- and R1- H, is dissolved with toluene;Add Pd2(dba)3, three tertiary fourths
Base phosphine, sodium tert-butoxide;Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reacting 10 at 95~110 DEG C of reaction temperature
~24 hours, cool down and filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate compound I;
The chloro- 1,3,5- triazines of 2,4,6- tri- and R1- H mol ratio is 1:1.0~1.5, Pd2(dba)3With 2,4,6-
The mol ratio of three chloro- 1,3,5- triazines is 0.006~0.02:1, tri-butyl phosphine and 2,4,6- tri- chloro-1,3,5-triazines rub
You are than being 0.006~0.02:1, sodium tert-butoxide and 2, the mol ratio of 4,6- tri- chloro-1,3,5-triazines is 2.0~3.0:1;
Work as Ar1When being not singly-bound,
Specifically course of reaction is:
Under nitrogen atmosphere, weigh the chloro-1,3,5-triazines of raw material 2,4,6- tri- and be dissolved in DMF i.e. DMF
In, then willAnd palladium is added, mixture is stirred, aqueous potassium phosphate solution is added, by the mixed of above-mentioned reactant
Solution is closed to be heated to reflux 5-15 hours at 120-150 DEG C of reaction temperature;After reaction terminates, cooling adds water, filters mixture
And dried in vacuum drying chamber, gained residue crosses silicagel column purifying, obtains compound intermediate I;
The chloro- 1,3,5- triazines of 2,4,6- tri- withMol ratio be 1:1.0~1.5, Pd (OAc)2With
The mol ratio of the chloro- 1,3,5- triazines of 2,4,6- tri- is 0.001~0.02:1, K3PO4With rubbing for the chloro- 1,3,5- triazines of 2,4,6- tri-
You are than being 1.0~2.0:1, DMF consumption and 2, the ratio of 4,6- tri- chloro-1,3,5-triazines is 1g:10~20ml;
Second step:Under nitrogen atmosphere, weigh intermediate compound I and be dissolved in DMF, then willAnd palladium is added, mixture is stirred, aqueous potassium phosphate solution is added, the mixing of above-mentioned reactant is molten
Liquid is heated to reflux 10-24 hours at 120-150 DEG C of reaction temperature;Reaction terminate after, cooling add water, by mixture filter and
Dried in vacuum drying chamber, gained residue crosses silicagel column purifying, obtains compound intermediate II;
The intermediate compound I withMol ratio be 1:1.0~1.5, Pd (OAc)2With rubbing for intermediate compound I
You are than being 0.001~0.02:1, K3PO4Mol ratio with intermediate compound I is 1.0~2.0:The ratio of 1, DMF consumption and intermediate compound I
For 1g:10~20ml;
3rd step:Under nitrogen atmosphere, weigh intermediate II and be dissolved in DMF, then willAnd palladium is added, mixture is stirred, aqueous potassium phosphate solution is added, the mixing of above-mentioned reactant is molten
Liquid is heated to reflux 10-24 hours at 120-150 DEG C of reaction temperature;Reaction terminate after, cooling add water, by mixture filter and
Dried in vacuum drying chamber, gained residue crosses silicagel column purifying, obtains target compound;
The intermediate II withMol ratio be 1:1.0~1.5, Pd (OAc)2With intermediate II
Mol ratio is 0.001~0.02:1, K3PO4Mol ratio with intermediate II is 1.0~2.0:1, DMF consumption and intermediate II
Ratio is 1g:15~30ml.
The applicant additionally provides a kind of described to be had by the organic compound of core of triazine and benzimidazole for preparation
Organic electroluminescence devices.The applicant additionally provides a kind of illumination or display element, including described organic electroluminescence device.
The applicant additionally provides a kind of organic electroluminescence device, and the organic electroluminescence device includes at least one layer
Functional layer contains described using triazine and benzimidazole as the organic compound of core.
The applicant additionally provides a kind of organic electroluminescence device, including hole blocking layer/electron transfer layer, the sky
Cave barrier layer/electron transfer layer contains described using triazine and benzimidazole as the organic compound of core.
The applicant additionally provides a kind of organic electroluminescence device, including CPL layers, described CPL layers contain with triazine and
Benzimidazole is the organic compound of core.
The present invention is beneficial to be had technical effect that:
The structure of the organic compound of the present invention contains two kinds of rigid radicals of triazine and benzimidazole, improves material structure
Stability;On space structure, triazine 4 and 6 are strong electro benzimidazole group, and 2 are separated with hole group so that
Material has higher density, obtains higher refractive index;Simultaneously so that material of the present invention all has very high Tg temperature;
The evaporation temperature of material of the present invention under vacuum conditions is generally less than 350 DEG C, both ensure that material steams for a long time in volume production
Plating material is not decomposed, and influence of crust deformation of the heat radiation to evaporation MASK due to being deposited with temperature is reduced again.
Material of the present invention is applied in OLED at CPL layers, is not involved in the electronics and hole transport of device, but to material
Heat endurance, membrane crystallization and optical transport (high index of refraction) there is very high requirement.As above analyze, triazine and benzimidazole
For rigid radical, the stability of material is improved;High Tg temperature, it is ensured that material is not crystallized under filminess;Low steaming
Temperature is plated, is the premise that material can be applied to volume production;High refractive index is then that material of the present invention can apply to CPL layers main
Factor.
Material of the present invention is because with deep HOMO energy levels, high electron mobility can effectively stop hole or energy from hair
Photosphere is transferred to electronic shell side, so that the combined efficiency of hole and electronics in luminescent layer is improved, so as to lift OLED
Luminous efficiency and service life.The present invention is after applied to the CPL of OLED layers, and the light that can effectively lift OLED takes
Go out efficiency.To sum up, compound of the present invention has good application effect and industrialization prospect in OLED luminescent devices.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED;Wherein, 1, OLED base
Plate, 2, anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, hole blocking layer/electron transfer layer, 7, electronics
Implanted layer, 8, cathode layer, 9, CPL layers.
Fig. 2 is the refraction index test figure of compound 1;Fig. 3 is compound 17 and well known materials CBP film Acceleration study contrast
Figure.
Embodiment
Embodiment 1:The synthesis of intermediate compound I
Work as Ar1During for singly-bound,
Weigh the chloro- 1,3,5- triazines of raw material 2,4,6- tri- and R1- H, is dissolved with toluene;Add Pd2(dba)3, three tertiary fourths
Base phosphine, sodium tert-butoxide;Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reacting 10 at 95~110 DEG C of reaction temperature
~24 hours, cool down and filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate compound I;
The chloro- 1,3,5- triazines of 2,4,6- tri- and R1- H mol ratio is 1:1.0~1.5, Pd2(dba)3With 2,4,6-
The mol ratio of three chloro- 1,3,5- triazines is 0.006~0.02:1, tri-butyl phosphine and 2,4,6- tri- chloro-1,3,5-triazines rub
You are than being 0.006~0.02:1, sodium tert-butoxide and 2, the mol ratio of 4,6- tri- chloro-1,3,5-triazines is 2.0~3.0:1;
Work as Ar1When being not singly-bound,
Under nitrogen atmosphere, R is weighed1-Ar1Bromo-derivative is dissolved in tetrahydrofuran (THF), then will double (pinacol foundation) two
Boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate are added, and mixture are stirred, by above-mentioned reactant
Mixed solution be heated to reflux 5-10 hours at 70-90 DEG C of reaction temperature;After reaction terminates, add water cooling and by mixture
Filter and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, R is obtained1-Ar1Boric acid pinacol
Ester;
Under nitrogen atmosphere, weigh the chloro-1,3,5-triazines of raw material 2,4,6- tri- and be dissolved in DMF, then willAnd palladium add, stir mixture, add aqueous potassium phosphate solution, by the mixed solution of above-mentioned reactant in
It is heated to reflux at 120-150 DEG C of reaction temperature 5-15 hours;After reaction terminates, cooling adds water, filters mixture and in vacuum
Dried in drying box, gained residue crosses silicagel column purifying, obtains compound intermediate I;
The chloro- 1,3,5- triazines of 2,4,6- tri- withMol ratio be 1:1.0~1.5, Pd (OAc)2With
The mol ratio of the chloro- 1,3,5- triazines of 2,4,6- tri- is 0.001~0.02:1, K3PO4With rubbing for the chloro- 1,3,5- triazines of 2,4,6- tri-
You are than being 1.0~2.0:1, DMF consumption is 2,4,6- tri- chloro-1,3,5-triazines:DMF=1g:10~20ml;
By taking the synthesis of intermediate A 1 as an example
(1) in 250mL there-necked flasks, nitrogen is passed through, 0.02mol 4- bromine triphenylamines is added and is dissolved in 100ml tetrahydrofurans
(THF) in, then by double (pinacol foundation) two boron of 0.024mol, 0.0002mol (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro
Palladium (II) and 0.05mol potassium acetates are added, and mixture are stirred, by the mixed solution of above-mentioned reactant at 80 DEG C of reaction temperature
It is heated to reflux 5 hours;After reaction terminates, cool down and add 100ml water and mixture is filtered and dried in vacuum drying oven.
The residue obtained is crossed into silica gel column separating purification, triphenylamine -4- pinacol borates are obtained;HPLC purity 99.7%, is received
Rate 88.1%.
Elementary analysis structure (molecular formula C24H26BNO2):Theoretical value C, 77.64;H,7.06;B,2.91;N,3.77;O,
8.62 test values:C,77.67;H,7.05;B,2.92;N,3.75;O,8.61.ESI-MS(m/z)(M+):Theoretical value
371.21, measured value is 371.55.
(2) in 250mL there-necked flasks, nitrogen is passed through, the chloro-1,3,5-triazines of 0.02mol raw materials 2,4,6- tri- are added,
Then 150mlDMF, 0.024mol triphenylamine -4- pinacol borates, 0.0002mol palladiums, stirring add 0.03mol
K3PO4The aqueous solution, is heated to 130 DEG C, back flow reaction 10 hours, sample point plate, reaction is complete.Natural cooling, adds water, will mix
Thing is filtered and dried in vacuum drying chamber, and gained residue crosses silicagel column purifying, obtains compound intermediate A1;HPLC purity
99.4%, yield 83.9%.
Elementary analysis structure (molecular formula C21H14Cl2N4):Theoretical value C, 64.14;H,3.59;Cl,18.03;N,14.25;
Test value:C,64.15;H,3.58;Cl,18.04;N,14.23.ESI-MS(m/z)(M+):Theoretical value 392.06, measured value
For 392.38.
Turn into example so that intermediate A is 2-in-1
250ml there-necked flask, under the atmosphere for being passed through nitrogen, adds the chloro-1,3,5-triazines of 0.01mol 2,4,6- tri-,
0.015mol diphenylamines, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml
Toluene, is heated to reflux 24 hours, sample point plate, and reaction is complete;Natural cooling, filtering, filtrate revolving crosses silicagel column, obtains middle
Body A2, HPLC purity 99.1%, yield 75.2%.
Elementary analysis structure (molecular formula C15H10Cl2N4):Theoretical value C, 56.80;H,3.18;Cl,22.36;N,17.66;
Test value:C,56.81;H,3.15;Cl,22.37;N,17.67.ESI-MS(m/z)(M+):Theoretical value 316.03, measured value
For 316.45.
Intermediate compound I is prepared with intermediate A 1, A2 synthetic method, concrete structure is as shown in table 1.
Table 1
Embodiment 2:IntermediateSynthesis
Work as Ar2Or Ar3When being expressed as formula (3) structure,
(1) in 250mL there-necked flasks, be passed through nitrogen, add the bromo- benzimidazoles of 0.02mol raw materials 2-, 0.03mol iodobenzenes,
0.04mol sodium hydrides, 0.004mol cuprous iodides and 0.01mol Phens are dissolved in 100ml 1,3- dimethyl -2- imidazoles
In quinoline ketone, stirring reaction 20-30h after reaction terminates, adds water and extracted with dichloromethane, organic layer anhydrous sodium sulfate drying,
Mixture with petroleum ether and ethyl acetate is that eluent is eluted, and the volume ratio of eluent petrochina ether and ethyl acetate is 1:
100, column chromatography purifying obtains intermediate M;
(2) under nitrogen atmosphere, weigh intermediate M and be dissolved in tetrahydrofuran, then by Br-Ar2-B(OH)2And four (triphenyls
Phosphine) palladium addition, mixture is stirred, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction temperature
It is heated to reflux at 70-90 DEG C 10-20 hours;After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, and extract is with anhydrous
Sodium sulphate drying process, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, compound intermediate N is obtained;
(3) under nitrogen atmosphere, weigh intermediate N and be dissolved in DMF (DMF), then will double (pinacols
Foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and stirs mixture, and will be above-mentioned
The mixed solution of reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature;After reaction terminates, cool down and will mix
Compound is filtered and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, compound intermediate is obtained
IV;
Work as Ar2Or Ar3When being expressed as formula (4) structure,
(1) under nitrogen atmosphere, the bromo- benzimidazoles of 2- is weighed and are dissolved in tetrahydrofuran, then by Ar5-B(OH)2And four (three
Phenylphosphine) palladium addition, mixture is stirred, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction
It is heated to reflux at 70-90 DEG C of temperature 5-15 hours;After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, extract nothing
Aqueous sodium persulfate drying process, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, compound intermediate P is obtained;
(2) under nitrogen atmosphere, intermediate P, I-Ar are added2- Br, sodium hydride, cuprous iodide and Phen are dissolved in 1,
In 3- dimethyl-2-imidazolinones, stirring reaction 20-30h after reaction terminates, is added water and extracted with dichloromethane, and organic layer is used
Anhydrous sodium sulfate drying, the mixture with petroleum ether and ethyl acetate is eluent elution, and column chromatography purifying obtains intermediate Q;
(3) under nitrogen atmosphere, weigh intermediate Q and be dissolved in DMF (DMF), then will double (pinacols
Foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and stirs mixture, and will be above-mentioned
The mixed solution of reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature;After reaction terminates, cool down and will mix
Compound is filtered and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, compound intermediate is obtained
IV;
Work as Ar2Or Ar3When being expressed as formula (5) structure,
(1) under nitrogen atmosphere, raw material W, I-Ar are added7, sodium hydride, cuprous iodide and Phen be dissolved in 1,3- diformazans
In base -2- imidazolones, stirring reaction 20-30h after reaction terminates, adds water and extracted with dichloromethane, the anhydrous sulphur of organic layer
Sour sodium is dried, and the mixture with petroleum ether and ethyl acetate is eluent elution, and column chromatography purifying obtains intermediate X;
(2) under nitrogen atmosphere, weigh intermediate X and be dissolved in tetrahydrofuran, then by Ar6-B(OH)2And four (triphenylphosphine)
Palladium is added, and is stirred mixture, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction temperature 70-
It is heated to reflux at 90 DEG C 5-15 hours;After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, extract anhydrous slufuric acid
Sodium drying process, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, compound intermediate Y is obtained;
(3) under nitrogen atmosphere, weigh intermediate Y and be dissolved in DMF, then by Br-Ar2-B(OH)2And
Palladium is added, and is stirred mixture, aqueous potassium phosphate solution is added, by the mixed solution of above-mentioned reactant in reaction temperature 120-
It is heated to reflux at 150 DEG C 10-24 hours;After reaction terminates, cooling adds water, mixture is filtered and done in vacuum drying chamber
Dry, gained residue crosses silicagel column purifying, obtains Compound Compound intermediate Z;
(4) under nitrogen atmosphere, weigh intermediate Z and be dissolved in DMF (DMF), then will double (pinacols
Foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and stirs mixture, and will be above-mentioned
The mixed solution of reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature;After reaction terminates, cool down and will mix
Compound is filtered and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, compound intermediate is obtained
IV;
By taking the synthesis of intermediate B 5 as an example
(1) in 250mL there-necked flasks, it is passed through nitrogen, adds 0.02mol raw materials 2, the bromo- 1H- benzimidazoles of 5- bis-,
0.03mol iodobenzenes, 0.04mol sodium hydrides, 0.004mol cuprous iodides and 0.01mol Phens are dissolved in 100ml 1,3- bis-
In methyl -2- imidazolones, stirring reaction 20-30h after reaction terminates, adds water and extracted with dichloromethane, and organic layer is with anhydrous
Sodium sulphate is dried, and the mixture with petroleum ether and ethyl acetate is eluent elution, eluent petrochina ether and ethyl acetate
Volume ratio is 1:100, column chromatography purifying obtains intermediate X 1;HPLC purity 99.7%, yield 78.5%.
Elementary analysis structure (molecular formula C13H8Br2N2):Theoretical value C, 44.35;H,2.29;Br,45.40;N,7.96;Survey
Examination value:C,44.34;H,2.27;Br,45.42;N,7.97.ESI-MS(m/z)(M+):Theoretical value 349.91, measured value is
350.26。
(2) in 250mL there-necked flasks, nitrogen is passed through, 0.04mol intermediate Xs 1,100mlTHF, 0.05mol benzene boron is added
Then acid, 0.0004mol tetrakis triphenylphosphine palladiums, stirring adds 0.06mol K2CO3The aqueous solution (2M), is heated to 80 DEG C, returns
Stream reaction 10 hours, sample point plate, reaction is complete.Natural cooling, is extracted with 200ml dichloromethane, layering, and extract is with anhydrous
Sodium sulphate is dried, filtering, filtrate revolving, is crossed silicagel column purifying, is obtained intermediate Y1, HPLC purity 99.8%, yield 88.2%.
Elementary analysis structure (molecular formula C19H13BrN2):Theoretical value C, 65.35;H,3.75;Br,22.88;N,8.02;Survey
Examination value:C,65.36;H,3.77;Br,22.86;N,8.01.ESI-MS(m/z)(M+):Theoretical value 348.03, measured value is
348.41。
(3) in 500mL there-necked flasks, nitrogen is passed through, 0.05 intermediate Y1 is added and is dissolved in 300mlN, N- dimethyl formyls
In amine (DMF), then by double (pinacol foundation) two boron of 0.06mol, 0.0005mol (1,1 '-bis- (diphenylphosphine) ferrocene) two
Chlorine palladium (II) and 0.125mol potassium acetates are added, and mixture are stirred, by the mixed solution of above-mentioned reactant in reaction temperature
It is heated to reflux at 120-150 DEG C 10 hours;After reaction terminates, cool down and add 200ml water and filter mixture and in vacuum
Dried in baking oven.The residue obtained is crossed into silica gel column separating purification, compound intermediate B5 is obtained;HPLC purity
99.2%, yield 81.2%.
Elementary analysis structure (molecular formula C25H25BN2O2):Theoretical value C, 75.77;H,6.36;B,2.73;N,7.07;O,
8.07;Test value:C,75.76;H,6.35;B,2.75;N,7.08;O,8.06.ESI-MS(m/z)(M+):Theoretical value
396.20, measured value is 396.62.
Intermediate compound IV is prepared with the synthetic method of intermediate B 5, concrete structure is as shown in table 2.
Table 2
Embodiment 3:The synthesis of compound 1:
In 250mL there-necked flasks, nitrogen is passed through, 0.01mol intermediate As 1,150mlDMF, 0.03mol intermediates is added
Then B1,0.0002mol palladium, stirring add 0.02mol K3PO4The aqueous solution, is heated to 150 DEG C, back flow reaction 24 is small
When, sample point plate, reaction is complete.Natural cooling, is extracted with 200ml dichloromethane, and layering, extract is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silicagel column purifying, obtains target product, HPLC purity 99.2%, yield 65.4%.
Elementary analysis structure (molecular formula C59H40N8):Theoretical value C, 82.30;H,4.68;N,13.01;Test value:C,
82.30;H,4.67;N,13.03.ESI-MS(m/z)(M+):Theoretical value 860.34, measured value is 860.64.
Embodiment 4:The synthesis of compound 2:
In 250mL there-necked flasks, nitrogen is passed through, 0.01mol intermediate As 2,150mlDMF, 0.03mol intermediates is added
Then B1,0.0002mol palladium, stirring add 0.02mol K3PO4The aqueous solution, is heated to 150 DEG C, back flow reaction 24 is small
When, sample point plate, reaction is complete.Natural cooling, is extracted with 200ml dichloromethane, and layering, extract is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silicagel column purifying, obtains target product, HPLC purity 99.3%, yield 75.4%.
Elementary analysis structure (molecular formula C53H36N8):Theoretical value C, 81.10;H,4.62;N,14.28;Test value:C,
81.11;H,4.63;N,14.26.ESI-MS(m/z)(M+):Theoretical value 784.31, measured value is 784.65.
Embodiment 5:The synthesis of compound 8:
The preparation method be the same as Example 4 of compound 8, difference is to replace intermediate B 1 with intermediate B 2.
Elementary analysis structure (molecular formula C51H34N10):Theoretical value C, 77.84;H,4.36;N,17.80;Test value:C,
77.83;H,4.35;N,17.82.ESI-MS(m/z)(M+):Theoretical value 786.30, measured value is 786.68.
Embodiment 6:The synthesis of compound 11:
The preparation method be the same as Example 3 of compound 11, difference is to replace intermediate A 1 with intermediate A 3;With centre
Body B3 replaces intermediate B 1.
Elementary analysis structure (molecular formula C59H40N8):Theoretical value C, 82.30;H,4.68;N,13.01;Test value:C,
82.32;H,4.66;N,13.02.ESI-MS(m/z)(M+):Theoretical value 860.34, measured value is 860.72.
Embodiment 7:The synthesis of compound 13:
The preparation method be the same as Example 4 of compound 13, difference is to replace intermediate B 1 with intermediate B 4.
Elementary analysis structure (molecular formula C59H48N8):Theoretical value C, 81.54;H,5.57;N,12.89;Test value:C,
81.52;H,5.58;N,12.90.ESI-MS(m/z)(M+):Theoretical value 868.40, measured value is 868.75.
Embodiment 8:The synthesis of compound 17:
The preparation method be the same as Example 4 of compound 17, difference is to replace intermediate A 2 with intermediate A 4.
Elementary analysis structure (molecular formula C65H44N8):Theoretical value C, 83.31;H,4.73;N,11.96;Test value:C,
83.30;H,4.72;N,11.98.ESI-MS(m/z)(M+):Theoretical value 936.37, measured value is 936.72.
Embodiment 9:The synthesis of compound 19:
The preparation method be the same as Example 4 of compound 19, difference is to replace intermediate B 1 with intermediate B 5.
Elementary analysis structure (molecular formula C53H36N8):Theoretical value C, 81.10;H,4.62;N,14.28;Test value:C,
81.13;H,4.61;N,14.26.ESI-MS(m/z)(M+):Theoretical value 784.31, measured value is 784.68.
Embodiment 10:The synthesis of compound 22:
The preparation method be the same as Example 3 of compound 22, difference is to replace intermediate A 1 with intermediate A 5.
Elementary analysis structure (molecular formula C62H44N8):Theoretical value C, 82.64;H,4.92;N,12.44;Test value:C,
82.61;H,4.94;N,12.45.ESI-MS(m/z)(M+):Theoretical value 900.37, measured value is 900.72.
Embodiment 11:The synthesis of compound 26:
The preparation method be the same as Example 3 of compound 26, difference is to replace intermediate A 1 with intermediate A 6.
Elementary analysis structure (molecular formula C65H42N8O):Theoretical value C, 82.08;H,4.45;N,11.78;O,1.68;Test
Value:C,82.10;H,4.44;N,11.76;O,1.69.ESI-MS(m/z)(M+):Theoretical value 950.35, measured value is
950.76。
Embodiment 12:The synthesis of compound 30:
The preparation method be the same as Example 3 of compound 30, difference is to replace intermediate A 1, intermediate with intermediate A 7
B3 replaces intermediate B 1.
Elementary analysis structure (molecular formula C65H44N8):Theoretical value C, 83.31;H,4.73;N,11.96;Test value:C,
83.33;H,4.72;N,11.95.ESI-MS(m/z)(M+):Theoretical value 936.37, measured value is 936.69.
The organic compound of the present invention is used in luminescent device, as CPL layer materials, with high Tg (gamma transitions
Temperature) temperature, high index of refraction.The compounds of this invention 1,2,8,11,13,17,19,22,26 and 30 is carried out respectively hot property and
The test of refractive index, as shown in table 3, the refraction index test result of wherein compound 1 is as shown in Figure 2 for testing result.
Table 3
Note:Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries
Instrument) determine, 10 DEG C/min of heating rate;Refractive index is by ellipsometer (U.S.'s J.A.Woollam Co. models:ALPHA-SE) survey
Amount, is tested as atmospheric environment.
The materials, organic compound of the invention such as CBP, Alq3 and the TPBi applied at present from upper table data, contrast
With high glass transition temperature, high index of refraction, simultaneously because containing triazine and benzimidazole rigid radical, it is ensured that material
Heat endurance.Therefore, the present invention by the organic material of core of triazine and benzimidazole in the CPL layers applied to OLED
Afterwards, the light extraction efficiency of device can be effectively improved, and ensure that the long-life of OLED.
The OLED material of the invention synthesized is described in detail in device below by way of device embodiments 1~12 and device comparative example 1
Application effect in part.Device embodiments 2~12 of the present invention, device comparative example 1 device compared with device embodiments 1
Manufacture craft it is identical, and employed identical baseplate material and electrode material, the thickness of electrode material are also kept
Unanimously, except that the CPL layer materials in 2~10 pairs of devices of device embodiments are converted;Device embodiments 11,12 pairs of devices
Hole barrier/electron transport layer materials of part are converted, and the performance test results of each embodiment obtained device are as shown in table 4.
Device embodiments 1:As shown in figure 1, a kind of electroluminescent device, its preparation process includes:
A) the ito anode layer 2 on cleaning transparent OLED device substrate 1, clear with deionized water, acetone, EtOH Sonicate respectively
Wash each 15 minutes, then handled 2 minutes in plasma cleaner;
B) on ito anode layer 2, hole injection layer material HAT-CN is deposited with by vacuum evaporation mode, thickness is 10nm,
This layer is used as hole injection layer 3;
C) on hole injection layer 3, hole mobile material NPB is deposited with by vacuum evaporation mode, thickness is 80nm, the layer
For hole transmission layer 4;
D) luminescent layer 5 is deposited with hole transmission layer 4, CBP is as being used as material of main part, Ir (ppy)3It is used as doping material
Material, Ir (ppy)3Mass ratio with CBP is 1:9, thickness is 30nm;
E) on luminescent layer 5, electron transport material TPBI is deposited with by vacuum evaporation mode, thickness is 40nm, this layer
Organic material is used as hole barrier/electron transfer layer 6;
F) on hole barrier/electron transfer layer 6, vacuum evaporation electron injecting layer LiF, thickness is 1nm, and the layer is electricity
Sub- implanted layer 7;
G) on electron injecting layer 7, vacuum evaporation negative electrode Mg:Ag/Ag layers, Mg:Ag doping ratios are 9:1, thickness
15nm, Ag thickness 3nm, the layer are cathode layer 8;
H) on cathode layer 8, CPL material compounds 1 are deposited with by vacuum evaporation mode, thickness is 50nm, and this layer has
Machine material is used as CPL layers 9.
After the making that electroluminescent device is completed according to above-mentioned steps, the current efficiency of measurement device and life-span, its result
It is shown in Table 4.The molecular machinery formula of associated materials is as follows:
Device embodiments 2:The CPL layer materials of electroluminescent device are changed into the compounds of this invention 2.Device embodiments 3:It is electroluminescent
The CPL layer materials of luminescent device are changed into the compounds of this invention 8.Device embodiments 4:The CPL layer materials of electroluminescent device are changed into
The compounds of this invention 11.Device embodiments 5:The CPL layer materials of electroluminescent device are changed into the compounds of this invention 13.Device is implemented
Example 6:The CPL layer materials of electroluminescent device are changed into the compounds of this invention 17.Device embodiments 7:The CPL layers of electroluminescent device
Material is changed into the compounds of this invention 19.Device embodiments 8:The CPL layer materials of electroluminescent device are changed into the compounds of this invention 22.
Device embodiments 9:The CPL layer materials of electroluminescent device are changed into the compounds of this invention 26.Device embodiments 10:Electroluminescent cell
The CPL layer materials of part are changed into the compounds of this invention 30.Device embodiments 11:Hole barrier/electric transmission of electroluminescent device
Layer material is changed into the compounds of this invention 7.Device embodiments 12:The hole barrier of electroluminescent device/electron transport layer materials become
For the compounds of this invention 27.Device comparative example 1:The CPL layer materials of electroluminescent device are changed into well known materials Alq3.Gained is electroluminescent
The detection data of luminescent device are shown in Table 4.
Table 4
It can be seen that and of the present invention be applied to by the organic compound of core of triazine and benzimidazole by the result of table 4
After OLED luminescent devices make, compared with device comparative example 1, light takes out and is obviously improved, and under same current density, device is bright
Degree and device efficiency are obtained for lifting, and because brightness and efficiency get a promotion, power consumption of the OLED in the case where determining brightness is relative
Reduction, service life is also improved.
In order to illustrate material membrane phase crystallization-stable performance of the present invention, by material compound 17 of the present invention and well known materials
CBP has carried out film and has accelerated crystallization experiment:Using vacuum evaporation mode, it is deposited with compound 17 and CBP evaporations respectively in alkali-free glass
On glass, and it is packaged in glove box (water oxygen content < 0.1ppm), by sample after encapsulation in double 85 (85 DEG C of temperature, humidity
85%) placed under the conditions of, the crystalline state of material membrane periodically observed with microscope (LEICA, DM8000M, 5*10 multiplying power),
As shown in table 5, material surface form is as shown in Figure 3 for experimental result:
Table 5
Title material | Compound 17 | CBP |
After material filming | Smooth surface morphology even uniform | Smooth surface morphology even uniform |
After experiment 72 hours | Smooth surface morphology even uniform, nodeless mesh | Surface forms some scattered circular crystal planes |
After experiment 600 hours | Smooth surface morphology even uniform, nodeless mesh | Surface checking |
Above description of test, the membrane crystallization stability of material of the present invention is significantly larger than well known materials, applied to OLED devices
Service life after part has beneficial effect.
Claims (8)
1. it is a kind of using triazine and benzimidazole as the organic compound of core, it is characterised in that the structure of the organic compound
As shown in formula (1):
In formula (1), Ar1、Ar2、Ar3Independently be expressed as C1-10Straight or branched alkyl;Halogen atom, protium, deuterium, tritium are former
The substituted or unsubstituted phenyl of son;Naphthyl;Dibiphenylyl;Terphenyl;Anthryl;Or one kind in pyridine radicals;Ar1、Ar2、Ar3
Can also be independently be expressed as singly-bound;
Ar1、Ar2、Ar3Can be with identical or different;
In formula (1), R1It is expressed as structure shown in formula (2);
In formula (2), R4、R5Independently be expressed as C1-10Straight or branched alkyl;Halogen atom, protium, deuterium, tritium atom take
Generation or unsubstituted phenyl;Naphthyl;Dibiphenylyl;Terphenyl;Anthryl;Pyridine radicals;Dibenzofurans;Dibenzothiophenes;9,
9- dimethyl fluorenes;Or one kind in N- phenyl carbazoles;
R4、R5Can be with identical or different;
In formula (1), R2、R3Independently be expressed as formula (3), formula (4) or structure shown in formula (5);
Wherein, Ar4、Ar5、Ar6、Ar7Independently be expressed as C1-10Straight or branched alkyl;Halogen atom replaces or unsubstituted
Phenyl;Naphthyl;Dibiphenylyl;Terphenyl;Or one kind in pyridine radicals;
R2、R3Can be with identical or different.
2. organic compound according to claim 1, it is characterised in that the concrete structure formula of the organic compound is:
In any one.
3. the preparation method of the organic compound described in a kind of claim 1 or 2, it is characterised in that occur in preparation process
Reaction equation is:
Work as Ar1During for singly-bound,
Specifically course of reaction is:
Weigh the chloro- 1,3,5- triazines of raw material 2,4,6- tri- and R1- H, is dissolved with toluene;Add Pd2(dba)3, tri-butyl phosphine,
Sodium tert-butoxide;Under an inert atmosphere, it is the mixed solution of above-mentioned reactant is small in reaction 10~24 at 95~110 DEG C of reaction temperature
When, cool down and filtering reacting solution, filtrate revolving crosses silicagel column, obtains intermediate compound I;
The chloro- 1,3,5- triazines of 2,4,6- tri- and R1- H mol ratio is 1:1.0~1.5, Pd2(dba)3It is chloro- with 2,4,6- tri-
The mol ratio of 1,3,5- triazines is 0.006~0.02:1, tri-butyl phosphine and 2, the mol ratio of 4,6- tri- chloro-1,3,5-triazines is
0.006~0.02:1, sodium tert-butoxide and 2, the mol ratio of 4,6- tri- chloro-1,3,5-triazines is 2.0~3.0:1;
Work as Ar1When being not singly-bound,
Specifically course of reaction is:
Under nitrogen atmosphere, weigh the chloro-1,3,5-triazines of raw material 2,4,6- tri- and be dissolved in DMF i.e. DMF, then
WillAnd palladium is added, mixture is stirred, aqueous potassium phosphate solution is added, by the mixed solution of above-mentioned reactant
It is heated to reflux 5-15 hours at 120-150 DEG C of reaction temperature;After reaction terminates, cooling adds water, filters mixture and true
Dried in empty drying box, gained residue crosses silicagel column purifying, obtains compound intermediate I;
The chloro- 1,3,5- triazines of 2,4,6- tri- withMol ratio be 1:1.0~1.5, Pd (OAc)2With 2,4,
The mol ratio of the chloro- 1,3,5- triazines of 6- tri- is 0.001~0.02:1, K3PO4With the mol ratio of the chloro- 1,3,5- triazines of 2,4,6- tri-
For 1.0~2.0:1, DMF consumption and 2, the ratio of 4,6- tri- chloro-1,3,5-triazines is 1g:10~20ml;
Second step:Under nitrogen atmosphere, weigh intermediate compound I and be dissolved in DMF, then willAnd
Palladium is added, and is stirred mixture, aqueous potassium phosphate solution is added, by the mixed solution of above-mentioned reactant in reaction temperature 120-
It is heated to reflux at 150 DEG C 10-24 hours;After reaction terminates, cooling adds water, mixture is filtered and done in vacuum drying chamber
Dry, gained residue crosses silicagel column purifying, obtains compound intermediate II;
The intermediate compound I withMol ratio be 1:1.0~1.5, Pd (OAc)2Mol ratio with intermediate compound I is
0.001~0.02:1, K3PO4Mol ratio with intermediate compound I is 1.0~2.0:The ratio of 1, DMF consumption and intermediate compound I is 1g:10
~20ml;
3rd step:Under nitrogen atmosphere, weigh intermediate II and be dissolved in DMF, then willAnd
Palladium is added, and is stirred mixture, aqueous potassium phosphate solution is added, by the mixed solution of above-mentioned reactant in reaction temperature 120-
It is heated to reflux at 150 DEG C 10-24 hours;After reaction terminates, cooling adds water, mixture is filtered and done in vacuum drying chamber
Dry, gained residue crosses silicagel column purifying, obtains target compound;
The intermediate II withMol ratio be 1:1.0~1.5, Pd (OAc)2With the mol ratio of intermediate II
For 0.001~0.02:1, K3PO4Mol ratio with intermediate II is 1.0~2.0:The ratio of 1, DMF consumption and intermediate II is
1g:15~30ml.
4. a kind of organic compound as claimed in claim 1 or 2 is used to prepare organic electroluminescence device.
5. a kind of organic electroluminescence device, it is characterised in that the organic electroluminescence device includes at least one layer of functional layer
Containing described in claim 1 or 2 using triazine and benzimidazole as the organic compound of core.
6. a kind of organic electroluminescence device, including hole blocking layer/electron transfer layer, it is characterised in that the hole barrier
Layer/electron transfer layer contain described in claim 1 or 2 using triazine and benzimidazole as the organic compound of core.
7. a kind of organic electroluminescence device, including CPL layers, it is characterised in that described CPL layers containing described in claim 1 or 2
Using triazine and benzimidazole as the organic compound of core.
8. one kind illumination or display element, it is characterised in that including organic electroluminescence device as claimed in claim 4.
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CN107513054A (en) * | 2017-09-29 | 2017-12-26 | 江苏三月光电科技有限公司 | It is a kind of using triazine and quinoxaline as the organic compound of core and its application on OLED |
CN108409721A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技(南京)有限公司 | A kind of luminous organic material and organic light emitting diode device |
CN110878091A (en) * | 2018-09-05 | 2020-03-13 | 江苏三月光电科技有限公司 | Organic compound based on triazine and anthrone structure and application thereof |
CN110922388A (en) * | 2018-09-19 | 2020-03-27 | 固安鼎材科技有限公司 | Novel compound and application thereof in organic electroluminescence field |
CN110818642A (en) * | 2018-12-10 | 2020-02-21 | 广州华睿光电材料有限公司 | Heterocyclic arylamine compound and application thereof in organic electronic device |
CN110845501A (en) * | 2018-12-10 | 2020-02-28 | 广州华睿光电材料有限公司 | Arylamine compound and application thereof in organic electronic device |
CN110818642B (en) * | 2018-12-10 | 2021-09-10 | 广州华睿光电材料有限公司 | Heterocyclic arylamine compound and application thereof in organic electronic device |
WO2020199996A1 (en) * | 2019-03-29 | 2020-10-08 | 吉林省元合电子材料有限公司 | Substituted 1,3,5-triazine compound, composition and application thereof |
TWI724832B (en) * | 2019-03-29 | 2021-04-11 | 大陸商吉林省元合電子材料有限公司 | Substituted 1,3,5-triazine compounds, compositions and applications thereof |
CN111943902A (en) * | 2020-08-21 | 2020-11-17 | 长春海谱润斯科技有限公司 | Triarylamine compound and organic light-emitting device thereof |
CN111943902B (en) * | 2020-08-21 | 2021-06-08 | 长春海谱润斯科技股份有限公司 | Triarylamine compound and organic light-emitting device thereof |
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