CN109485576A - Material for organic electroluminescent device and organic electroluminescence device comprising it - Google Patents
Material for organic electroluminescent device and organic electroluminescence device comprising it Download PDFInfo
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- CN109485576A CN109485576A CN201811343598.9A CN201811343598A CN109485576A CN 109485576 A CN109485576 A CN 109485576A CN 201811343598 A CN201811343598 A CN 201811343598A CN 109485576 A CN109485576 A CN 109485576A
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Abstract
The present invention provides a kind of material for organic electroluminescent device and the organic electroluminescence device comprising it, belongs to technical field of organic electroluminescence.Material for organic electroluminescent device provided by the invention, including material of main part and dopant material, the dopant material in the main structure of cyclopropane by connecting the groups such as aryl, heteroaryl or fluorenes alkene, on the one hand the molecular weight of compound is increased, with high glass transition temperature, the conductivity of compound is on the other hand improved, increases the migration rate of carrier, and then the driving voltage of organic electroluminescence device is reduced, improve its service life.By dopant material of the invention with the benzidine host material combination of specific structure, the thermal stability of conductivity and entirety can be improved on the whole, reduce the driving voltage of organic electroluminescence device, and then improve the luminescent properties of organic electroluminescence device.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, and in particular to a kind of material for organic electroluminescent device and packet
Containing its organic electroluminescence device.
Background technique
Organic electroluminescent LED (Organic Light-Emitting Diode, OLED) refers to luminous organic material
The diode to shine under the action of electric current or electric field, electric energy can be converted into luminous energy by it.Kodak Company in 1987
Tang etc. has invented sandwich type organic bilayer film luminescent device, this breakthrough, allows it is seen that OLED technology
Great potential that is practical, moving towards commercial market is moved towards, the research boom of Organic Light Emitting Diode has been started.Over 30 years, OLED
Technology achieves development with rapid changepl. never-ending changes and improvements, moves towards the industrialization production from laboratory research.All solid state, the active of OLED technology
Shine, high contrast, it is ultra-thin, can Flexible Displays, low-power consumption, wide viewing angle, fast response time, operating temperature range is wide, it is real to be easy to
Many advantages, such as existing 3D display, " fantasy display " is known as by insider, will become following most potential new
Type display technology.
But for the actual demand of current organic electroluminescent industry, the development of electroluminescent organic material lags behind face
The requirement of plate manufacturing enterprise, therefore as material type enterprise, developing, there is the organic functional material of higher performance to seem especially heavy
It wants.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provide a kind of material for organic electroluminescent device and comprising
Its organic electroluminescence device.
The present invention provides a kind of material for organic electroluminescent device, including material of main part and dopant material, the masters
Body material has structure shown in formula (I):
Wherein, Ar1、Ar2The independent aryl for being 6~25 selected from carbon atom number；R1、R2、R3、R4、R5It is independent selected from hydrogen,
Deuterium, the alkyl that carbon atom number is 1~4；X is independent to be selected from hydrogen, cyano or trifluoromethyl；
The dopant material has structure shown in formula (II):
Wherein, R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl, substituted or unsubstituted C6~C30
Aryl, substituted or unsubstituted C3~C30 heteroaryl orOne of or R6With R7、R8With R9、R10
With R11Between independently condense cyclization；
R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1~C10 alkyl, substituted or unsubstituted
The aryl of C6~C30, one of the heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer；
R12~R14Independently selected from one of halogen, nitro, cyano or trifluoromethyl.
Preferably, in material of main part shown in formula (I), Ar1、Ar2It is independent selected from phenyl, it is terphenyl, fluorenyl, Spirofluorene-based
Or fluoranthene base.
Preferably, in material of main part shown in formula (I), R1、R2、R3、R4、R5Independent hydrogen, deuterium, the carbon atom number of being selected from is 1~4
Alkyl.
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl,
Substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted three
Piperazine base orOne of, wherein R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1
The alkyl of~C10, the aryl of substituted or unsubstituted C6~C30, substituted or unsubstituted C3~C30 heteroaryl in one
Kind；
M, n independently selected from 0 to 4 integer.
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from cyano, trifluoromethyl orOne of, wherein R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1~C4
One of alkyl, the aryl of substituted or unsubstituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer.
Preferably, in dopant material shown in formula (II), R15、R16Independently selected from hydrogen, halogen, nitro, cyano, fluoroform
Base, methyl, ethyl, isopropyl, tert-butyl, phenyl, xenyl or pyridyl group.
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from cyano, trifluoromethyl or knot as follows
Any one of structure:
Preferably, in dopant material shown in formula (II), R6、R8、R10In at least one be cyano or trifluoromethyl.
Preferably, in dopant material shown in formula (II), R6With R7、R8With R9、R10With R11Between be independently fused into substitution or
Unsubstituted pyridine.
The present invention also provides a kind of organic electroluminescence device, including anode, cathode and be located at the anode with it is described
One layer or more of organic matter layer between cathode, at least one layer in described one layer or more of organic matter layer include described organic
Electroluminescent device material.
Beneficial effects of the present invention:
Material for organic electroluminescent device provided by the invention, including material of main part and dopant material, the doping material
On the one hand material increases point of compound by connecting the groups such as aryl, heteroaryl or fluorenes alkene in the main structure of cyclopropane
Son amount, with high glass transition temperature, on the other hand improves the conductivity of compound, increases the migration speed of carrier
Rate, and then the driving voltage of organic electroluminescence device is reduced, improve its service life.Further, the introducing of fluorenes alkenyl group, making
Closing object integrally has spatial configuration, and the film forming of material is more preferable, and is not easy to crystallize.Further, compound entirety has
There is asymmetry, crystallization can be further reduced.Further, by introducing R in fluorenes alkenyl group15、R16Substituent group
Group, can increase the dissolubility of compound, can be molten using spin coating, inkjet printing etc. when preparing organic electroluminescence device
A variety of methods such as liquid coating or vacuum evaporation.By dopant material of the invention and with the benzidine material of main part group of specific structure
It closes, the thermal stability of conductivity and entirety can be improved on the whole, reduce the driving voltage of organic electroluminescence device, in turn
Improve the luminescent properties of organic electroluminescence device.
Specific embodiment
It is clearly and completely described below in conjunction with the technical solution of the specific embodiment of the invention, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Technical staff's every other embodiment obtained without making creative work, belongs to protection model of the invention
It encloses.
It should be noted that unless otherwise prescribed, the meaning of scientific and technical terminology used in the present invention and those skilled in the art
The meaning that member is generally understood is identical.
Aryl of the present invention refers to remove a hydrogen atom on an aromatic core carbon of aromatic hydrocarbon molecule after, remaining group
General name, can be monocyclic aryl or fused ring aryl, such as can be selected from phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthrene
Base, pyrenyl, fluorenyl or benzo phenanthryl etc., but not limited to this.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are replaced by hetero atom
General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, such as pyridyl group, quinolyl, carbazyl, thienyl, benzothienyl, furyl, benzofuranyl, pyrimidine can be selected from
Base, benzo pyrimidine radicals, imidazole radicals or benzimidazolyl etc., but not limited to this.
Alkyl of the present invention refers to alkyl made of minusing one or several hydrogen atoms in alkane molecule, can be straight
Alkyl group, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl,
Tert-butyl, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Condensed cyclization of the present invention refers to that two groups are connected to each other by chemical bond.It is as follows:
In the present invention, the ring being fused into can be five-membered ring or hexatomic ring, such as phenyl, naphthalene, hexamethylene and phenyl, quinoline
Quinoline base, isoquinolyl, dibenzothiophene, phenanthryl or pyrenyl, but not limited to this.
It is described present invention firstly provides a kind of material for organic electroluminescent device, including material of main part and dopant material
Material of main part has structure shown in formula (I):
Wherein, Ar1、Ar2The independent aryl for being 6~25 selected from carbon atom number；R1、R2、R3、R4、R5It is independent selected from hydrogen,
Deuterium, the alkyl that carbon atom number is 1~4；X is independent to be selected from hydrogen, cyano or trifluoromethyl；
The dopant material has structure shown in formula (II):
Wherein, R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl, substituted or unsubstituted C6~C30
Aryl, substituted or unsubstituted C3~C30 heteroaryl orOne of or R6With R7、R8With R9、R10
With R11Between independently condense cyclization；
R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1~C10 alkyl, substituted or unsubstituted
The aryl of C6~C30, one of the heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer；
R12~R14Independently selected from one of halogen, nitro, cyano or trifluoromethyl.
Heretofore described " substituted or unsubstituted ", the substituent group is independent to be selected from D-atom, cyano, nitro, halogen
Plain atom, the alkyl of C1-C10, the alkoxy of C1-C10, the alkylthio group of C1-C10, the aryl of C6-C30, C6-C30 fragrant oxygen
Base, the arylthio of C6-C30, C3-C30 heteroaryl, the silylation of C1~C30, the alkylamino radical of C2~C10, C6~C30 virtue
Amido etc., for example, D-atom, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxyl group, methyl mercapto,
Phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl, base, pyrenyl, fluorenyl, 9,9- dimethyl fluorenyl, benzene
Methyl, phenoxy group, thiophenyl, hexichol amido, dimethylamino, carbazyl, 9- phenyl carbazole base, furyl, thienyl, triphenyl
Silicon substrate, trimethyl silicon substrate, trifluoromethyl, phenothiazinyl, phenoxazine base, acridinyl, piperidyl, pyridyl group, pyrazinyl, triazine
Base, pyrimidine radicals etc., but not limited to this.
According to the present invention, the dopant material and the material of main part are preferably doped with 1%~15% concentration, more
Preferably 2%~10%, most preferably 3%~7%.
Preferably, in material of main part shown in formula (I), Ar1、Ar2It is independent selected from phenyl, it is terphenyl, fluorenyl, Spirofluorene-based
Or fluoranthene base.Preferably, in material of main part shown in formula (I), R1、R2、R3、R4、R5It is independent selected from hydrogen, deuterium, carbon atom number be 1~
4 alkyl.
Preferably, any one of material of main part shown in formula (I) in structure shown in following TM1~TM24:
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl,
Substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted three
Piperazine base orOne of, wherein R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1
The alkyl of~C10, the aryl of substituted or unsubstituted C6~C30, substituted or unsubstituted C3~C30 heteroaryl in one
Kind；
M, n independently selected from 0 to 4 integer.
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from cyano, trifluoromethyl orOne of, wherein R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, C1~C4
One of alkyl, the aryl of substituted or unsubstituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer.
Preferably, in dopant material shown in formula (II), R15、R16Independently selected from hydrogen, halogen, nitro, cyano, fluoroform
Base, methyl, ethyl, isopropyl, tert-butyl, phenyl, xenyl or pyridyl group.
Preferably, in dopant material shown in formula (II), R6~R11Independently selected from cyano, trifluoromethyl or knot as follows
Any one of structure:
Preferably, in dopant material shown in formula (II), R6、R8、R10In at least one be cyano or trifluoromethyl.
Preferably, in dopant material shown in formula (II), R6With R7、R8With R9、R10With R11Between be independently fused into substitution or
Unsubstituted pyridine.
Preferably, any one of dopant material in structure as follows shown in formula (II):
Some specific constructive forms of material of main part and dopant material of the present invention are enumerated above, but the present invention is not
These listed chemical structures are confined to, all based on structure shown in formula (I) and formula (II), substituent group is as defined above
Group should be all included.
Compound shown in formula (I) of the present invention can be prepared by following synthetic route:
Wherein, Ar1、Ar2、R1、R2、R3、R4、R5Restriction with X is as described above, details are not described herein
According to the present invention, intermediate A and intermediate B compound represented are prepared according to method as follows:
Under nitrogen protection, palladium acetate and tri-tert-butylphosphine are catalyst, in the case that sodium tert-butoxide is alkali, by aromatic series
Amine is reacted with shown halides, obtains corresponding intermediate.
According to the present invention, compound shown in formula (I) is prepared according to method as follows:
(1) under nitrogen protection, palladium acetate and tri-tert-butylphosphine are catalyst, in the case that sodium tert-butoxide is alkali, will in
Mesosome A is reacted with shown dibromo substituent, obtains intermediate C；
(2) under nitrogen protection, palladium acetate and tri-tert-butylphosphine are catalyst, in the case that sodium tert-butoxide is alkali, will in
Mesosome B is reacted with intermediate C, obtains compound shown in target product formula (I).
The preparation method of organic electroluminescence device compound of the present invention, can be by by tetrachloro cyclopropylene and containing
R6~R14The substance of group reacts in the presence such as lithium hydride and glycol dimethyl ether to be completed, however, the present invention is not limited thereto.This hair
The bright reaction condition to above-mentioned reaction does not have special limitation, using reaction condition well-known to those skilled in the art.
The present invention is not particularly limited the source of raw material employed in above-mentioned each reaction, for commercial product or can use ability
The preparation of preparation method known to field technique personnel, which is voluntarily prepared or customized, to be obtained.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device is those skilled in the art
Known organic electroluminescence device, organic electroluminescence device of the present invention include anode, cathode and are located at
One layer or more of organic matter layer between the anode and the cathode, at least one layer in described one layer or more of organic matter layer
Include the organic electroluminescence device compound.
The organic matter may include hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole resistance layer by layer
At least one layer in barrier, electron transfer layer and electron injecting layer, it is preferred that the organic matter comprising the organic luminescent compounds
Layer is hole injection layer or hole transmission layer.
About organic electroluminescence device of the invention, in addition at least one layer packet in described one layer or more of organic matter layer
Other than the organic electroluminescence device compound, material as known in the art and method can use to make
It makes.
The present invention is not particularly limited the source of raw material employed in following embodiment, can for commercial product or
It is prepared using preparation method well-known to those skilled in the art.
Embodiment 1: the preparation of compound TM1
(1) preparation of intermediate A 1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium acetate (0.4g, 1.83mmol) and uncle
Sodium butoxide (22.8g, 238mmol) is added to aniline (17.0g, 183mmol) and 4- bromine para-terpheny (56.3g, 183mmol) exists
Solution in degassed toluene (500mL), and the mixture is heated 2 hours under reflux.The reaction mixture is cooled to
Room temperature is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and is merged organic
It is evaporated by phase under vacuum.The residue is filtered via silica gel (heptane/methylene chloride), and from isopropanol
Middle crystallization.Obtain the A1 (52.8g, theoretical value 90%) of solid form.
(2) preparation of intermediate B 1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium acetate (0.4g, 1.83mmol) and uncle
Sodium butoxide (22.8g, 238mmol) is added to 2- bromo biphenyl (42.4g, 183mmol) and 2- aminobphenyl (30.9g, 183mmol)
Solution in degassed toluene (500mL), and the mixture is heated 2 hours under reflux.The reaction mixture is cooling
To room temperature, filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and is associated with
It is evaporated by machine phase under vacuum.The residue is filtered via silica gel (heptane/methylene chloride), and from isopropyl
It is crystallized in alcohol.Obtain the B1 (47.8g, theoretical value 92%) of solid form.
(3) synthesis of intermediate C1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium acetate (0.4g, 1.83mmol) and uncle
Sodium butoxide (52.7g, 549mmol) is added to 4,4- '-dibromobiphenyl (56.7g, 183mmol) and A1 (58.7g, 183mmol) de-
Solution in gas toluene (500mL), and the mixture is heated 2 hours under reflux.The reaction mixture is cooled to room
Temperature is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase,
It is evaporated under vacuum.The residue is filtered via silica gel (heptane/methylene chloride), and is tied from isopropanol
It is brilliant.Obtain the C1 (87.5g, theoretical value 85%) of solid form.
(4) synthesis of target product TM1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium acetate (0.4g, 1.83mmol) and uncle
Sodium butoxide (52.7g, 549mmol) is added to C1 (103.0g, 183mmol) and B1 (61.6g, 192mmol) in degassed toluene
Solution in (500mL), and the mixture is heated 2 hours under reflux.The reaction mixture is cooled to room temperature, first is used
Benzene is diluted and is filtered via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase, by its
It is evaporated under vacuum.The residue is filtered via silica gel (heptane/methylene chloride), and is crystallized from isopropanol.?
To the TM1 (123.2g, theoretical value 85%) of solid form.
Mass spectrum m/z:792.31 (calculated value: 792.35).Theoretical elemental content (%) C60H44N2: C, 90.87；H,5.59；
N, 3.53 actual measurement constituent content (%): C, 90.88；H,5.58；N,3.54.The above results confirm that obtaining product is target product.
Embodiment 2: the preparation of compound TM4
B-1 in embodiment 1 is replaced with into B-2 as shown above, obtains compound TM4.Mass spectrum m/z:802.38 (calculated value:
802.41).Theoretical elemental content (%) C60H34D10N2: C, 89.74；H,6.78；N, 3.49 actual measurement constituent content (%): C,
89.73；H,6.79；N,3.48.The above results confirm that obtaining product is target product.
Embodiment 3: the preparation of compound TM5
B-1 in embodiment 1 is replaced with into B-3 as shown above, obtains compound TM5.Mass spectrum m/z:848.43 (calculated value:
848.41).Theoretical elemental content (%) C64H52N2: C, 90.53；H,6.17；N, 3.30 actual measurement constituent content (%): C, 90.52；
H,6.17；N,3.31.The above results confirm that obtaining product is target product.
Embodiment 4: the preparation of compound TM7
A-1 in embodiment 1 is replaced with into A-2 as shown above, C-1 replaces with C-2 as shown above, obtains compound TM7.Matter
Compose m/z:756.37 (calculated value: 756.35).Theoretical elemental content (%) C57H44N2: C, 90.44；H,5.86；N, 3.70 actual measurements
Constituent content (%): C, 90.43；H,5.86；N,3.71.The above results confirm that obtaining product is target product.
Embodiment 5: the preparation of compound TM10
A-1 in embodiment 1 is replaced with into A-2 as shown above, C-1 replaces with C-2 as shown above, and B-1 replaces with institute as above
Show B-2, obtains compound TM10.Mass spectrum m/z:766.45 (calculated value: 766.41).Theoretical elemental content (%) C57H34D10N2:
C,89.25；H,7.09；N, 3.65 actual measurement constituent content (%): C, 89.24；H,7.09；N,3.67.The above results confirm to obtain
Product is target product
Embodiment 6: the preparation of compound TM11
A-1 in embodiment 1 is replaced with into A-2 as shown above, C-1 replaces with C-2 as shown above, and B-1 replaces with institute as above
Show B-3, obtains compound TM11.Mass spectrum m/z:812.42 (calculated value: 812.41).Theoretical elemental content (%) C61H52N2: C,
90.11；H,6.45；N, 3.45 actual measurement constituent content (%): C, 90.12；H,6.43；N,3.45.The above results confirmation is produced
Object is target product.
Embodiment 7: the preparation of compound TM19
A-1 in embodiment 1 is replaced with into A-3 as shown above, C-1 replaces with C-3 as shown above, obtains compound TM19.
Mass spectrum m/z:878.35 (calculated value: 878.37).Theoretical elemental content (%) C67H46N2: C, 91.54；H,5.27；N, 3.19 is real
Survey constituent content (%): C, 91.53；H,5.28；N,3.19.The above results confirm that obtaining product is target product.
Embodiment 8: the preparation of compound TM22
A-1 in embodiment 1 is replaced with into A-3 as shown above, C-1 replaces with C-3 as shown above, and B-1 replaces with institute as above
Show B-2, obtains compound TM22.Mass spectrum m/z:888.42 (calculated value: 888.43).Theoretical elemental content (%) C67H36D10N2:
C,90.50；H,6.35；N, 3.15 actual measurement constituent content (%): C, 90.52；H,6.34；N,3.14.The above results confirm to obtain
Product is target product.
Embodiment 9: the preparation of compound 1
Step 1: cooling to -80 DEG C under Ar protection, 1.6M being added just the anhydrous tetrahydro furan (20ml) in stirring
The hexane solution (13.4ml, 21.46mmol) of butyl lithium, is subsequently added into and is mixed with the four of succinonitrile (1.56g, 19.51mmol)
Hydrogen furans (15ml).Reaction solution the reaction was continued at -80 DEG C 1h, obtains white suspension, and within the time of 5min, Fluorenone is added dropwise
The tetrahydrofuran solution (20ml) of (3.55g, 19.5mmol) continues stirring 30 minutes.Ice bath is removed, reaction solution presents faint yellow
Solution pours into reaction solution in the mixed liquor of ice water and hydrochloric acid, continues to stir, static rear reaction liquid layer.Collect organic phase, water
It is mutually extracted with ethyl acetate, merges organic phase, dry with anhydrous sodium sulfate, concentration obtains crude product.By column chromatography (petroleum ether/
Ethyl acetate, 8.5:1.5), obtain white intermediate II (4.3g, 16.5mmol), yield 87%.
Step 2: under Ar gas shielded, to the dry methylene chloride solution 30ml of intermediate II (4.07g, 15.6mmol)
In, dry pyridine (1.50ml, 18.52mmol) is added, reaction solution is then cooled to 0 DEG C with ice salt bath, reacts 20min.
Under conditions of 0 DEG C, thionyl chloride (1.27ml, 17.42mmol) is added in 10min, it is small to be gradually warming up to room temperature the reaction was continued 3
When.After the reaction was completed, mixture of ice and water 10ml, methylene chloride 30ml is added, separates organic phase, successively uses dilute hydrochloric acid, water and carbon
Sour hydrogen sodium (5%, 15ml) washing.Organic phase is separated, dry with anhydrous sodium sulfate, concentration obtains crude product, chromatographs (stone by column
Oily ether/ethyl acetate, 9.9:0.1) obtain intermediate compound I, yield 92%.
Step 3: 98% lithium hydride of 4.4 equivalents is added in the glycol dimethyl ether of 60ml, it is cooled to 0 DEG C.?
Intermediate compound I (3.38g, 15.0mmol) is dissolved in the glycol dimethyl ether of 6ml, and is added dropwise in 1min.Remove ice
Bath, reaction solution is gradually warming up to room temperature, and reacts 15min at room temperature.Reaction solution is again cooled to 0 DEG C, by tetrachloro cyclopropylene
The ethylene glycol dimethyl ether solution 4ml of (0.712g, 4mmol) is instilled in reaction solution.Reaction solution gradually becomes kermesinus, is warming up to
Room temperature continues stirring 44 hours.Reaction solution is poured into the ice water of 1.2L, obtained mixed liquor concentrated hydrochloric acid adjusts pH value to 1
(about addition 24ml hydrochloric acid), is then extracted with 3 × 50ml ethyl acetate, merges organic phase, successively use saturated salt solution, deionization
Water, sodium bicarbonate aqueous solution washing, are finally washed with deionized primary again.Organic phase is dry with anhydrous sodium sulfate, is concentrated, and obtains
To dark crude product.The crude product continues directly to react without purification.
Above-mentioned dark crude product is dissolved into the glacial acetic acid of 140ml, the mixed acid solution (mixed acid solution of hydrochloric acid and nitric acid is added
Prepare as follows: by 36ml, 48% dilute hydrochloric acid and 12ml, 65% concentrated nitric acid mixing, current existing system), mixed liquor continues to stir
1.5 hours, filtering, obtained orange filter cake was washed with deionized, is dried to obtain crude product, and the method for crude product distillation obtains most
Finished product (1.15g, 1.52mmol), yield 38% (on the basis of tetrachloro cyclopropylene).Mass spectrum m/z:756.29 (calculated value:
756.21).Theoretical elemental content (%) C54H24N6: C, 85.70；H, 3.20；N, 11.10；Constituent content (%): C is surveyed,
85.75；H, 3.21；N, 11.12.It is target product 1 that above-mentioned confirmation, which obtains product,.
Embodiment 10: the preparation of compound 2
Fluorenone in embodiment 9 is replaced with into structure as above, obtains compound 2.Mass spectrum m/z:864.24 (calculated value:
864.15).Theoretical elemental content (%) C54H18F6N6: C, 75.00；H, 2.10；F, 13.18；N, 9.72；Survey constituent content
(%): C, 75.07；H, 2.10；F, 13.20；N, 9.73.It is target product 2 that above-mentioned confirmation, which obtains product,.
Embodiment 11: the preparation of compound 7
Fluorenone in embodiment 9 is replaced with into structure as above, obtains compound 7.Mass spectrum m/z:1092.69 (calculated value:
1092.58).Theoretical elemental content (%) C78H72N6: C, 85.68；H, 6.64；N, 7.69；Constituent content (%): C is surveyed,
85.74；H, 6.66；N, 7.72.It is target product 7 that above-mentioned confirmation, which obtains product,.
Embodiment 12: the preparation of compound 8
Succinonitrile in embodiment 9 is replaced with into 4,4,4- trifluoro-butyronitriles, obtains compound 8.Mass spectrum m/z:885.26 (meter
Calculation value: 885.18).Theoretical elemental content (%) C54H24F9N3: C, 73.22；H, 2.73；F, 19.30；N, 4.74；Survey element
Content (%): C, 73.26；H, 2.73；F, 19.33；N, 4.72.It is target product 8 that above-mentioned confirmation, which obtains product,.
Embodiment 13: the preparation of compound 15
Step 1: cooling to -80 DEG C under Ar protection, 1.6M being added just the anhydrous tetrahydro furan (20ml) in stirring
The hexane solution (13.4ml, 21.46mmol) of butyl lithium, is subsequently added into and is mixed with the four of succinonitrile (1.56g, 19.51mmol)
Hydrogen furans (15ml).Reaction solution the reaction was continued at -80 DEG C 1h, obtains white suspension, and within the time of 5min, Fluorenone is added dropwise
The tetrahydrofuran solution (20ml) of (3.55g, 19.5mmol) continues stirring 30 minutes.Ice bath is removed, reaction solution presents faint yellow
Solution pours into reaction solution in the mixed liquor of ice water and hydrochloric acid, continues to stir, static rear reaction liquid layer.Collect organic phase, water
It is mutually extracted with ethyl acetate, merges organic phase, dry with anhydrous sodium sulfate, concentration obtains crude product.By column chromatography (petroleum ether/
Ethyl acetate, 8.5:1.5), obtain white intermediate II (4.3g, 16.5mmol), yield 87%.
Step 2: under Ar gas shielded, to the dry methylene chloride solution of intermediate II (4.07g, 15.6mmol)
In (30ml), dry pyridine (1.50ml, 18.52mmol) is added, reaction solution is then cooled to 0 DEG C with ice salt bath, reaction
20min.Under conditions of 0 DEG C, thionyl chloride (1.27ml, 17.42mmol) is added in 10min, is gradually warming up to room temperature continuation
Reaction 3 hours.After the reaction was completed, be added mixture of ice and water 10ml, methylene chloride 30ml, separate organic phase, successively with dilute hydrochloric acid,
Water and sodium bicarbonate (5%, 15ml) washing.Organic phase is separated, dry with anhydrous sodium sulfate, concentration obtains crude product, passes through column
Chromatography (petrol ether/ethyl acetate, 9.9:0.1) obtains intermediate compound I (3.38g, 15.0mmol), yield 92%.
Step 3: 98% lithium hydride of 2.2 equivalents is added in the glycol dimethyl ether of 60ml, it is cooled to 0 DEG C.?
Intermediate compound I (1.85g, 8.2mmol) is dissolved in the glycol dimethyl ether of 6ml, and is added dropwise in 1min.Remove ice
Bath, reaction solution is gradually warming up to room temperature, and reacts 15min at room temperature.Reaction solution is again cooled to 0 DEG C, by tetrachloro cyclopropylene
The ethylene glycol dimethyl ether solution 4ml of (0.712g, 4mmol) is instilled in reaction solution.Reaction solution gradually becomes kermesinus, is warming up to
Room temperature continues stirring 44 hours.Reaction solution is poured into the ice water of 1.2L, obtained mixed liquor concentrated hydrochloric acid adjusts pH value to 1
(about addition 24ml hydrochloric acid), is then extracted with 3 × 50ml ethyl acetate, merges organic phase, successively use saturated salt solution, deionization
Water, sodium bicarbonate aqueous solution washing, are finally washed with deionized primary again.Organic phase is dry with anhydrous sodium sulfate, is concentrated, and obtains
To dark crude product.The crude product continues directly to react without purification.
Step 4: 98% lithium hydride of 2.2 equivalents is added in the glycol dimethyl ether of 60ml, it is cooled to 0 DEG C.Again
The crude product that upper step obtains is dissolved in the glycol dimethyl ether of 6ml, and is added dropwise in 1min.Remove ice bath, reaction solution
It is gradually warming up to room temperature, and reacts 15min at room temperature.Reaction solution is again cooled to 0 DEG C, by ptfe pyridine class raw material
The ethylene glycol dimethyl ether solution 4ml of (0.78g, 4.1mmol) is instilled in reaction solution.Reaction solution gradually becomes kermesinus, is warming up to
Room temperature continues stirring 44 hours.Reaction solution is poured into the ice water of 1.2L, obtained mixed liquor concentrated hydrochloric acid adjusts pH value to 1
(about addition 24ml hydrochloric acid), is then extracted with 3 × 50ml ethyl acetate, merges organic phase, successively use saturated salt solution, deionization
Water, sodium bicarbonate aqueous solution washing, are finally washed with deionized primary again.Organic phase is dry with anhydrous sodium sulfate, is concentrated, and obtains
To dark crude product.The crude product continues directly to react without purification.
Above-mentioned dark crude product is dissolved into the glacial acetic acid of 140ml, the mixed acid solution (mixed acid solution of hydrochloric acid and nitric acid is added
Prepare as follows: by 36ml, 48% dilute hydrochloric acid and 12ml, 65% concentrated nitric acid mixing, current existing system), mixed liquor continues to stir
1.5 hours, filtering, obtained orange filter cake was washed with deionized, is dried to obtain crude product, and the method for crude product distillation obtains most
Finished product (1.07g, 1.52mmol), yield 38% (on the basis of tetrachloro cyclopropylene).Mass spectrum m/z:704.19 (calculated value:
704.14).Theoretical elemental content (%) C44H16F4N6: C, 75.00；H, 2.29；F, 10.78；N, 11.93；Survey constituent content
(%): C, 75.07；H, 2.28；F, 10.77；N, 11.95.It is target product 15 that above-mentioned confirmation, which obtains product,.
Embodiment 14: the preparation of compound 18
Fluorenone in embodiment 13 is replaced with into structure as above, obtains compound 18.Mass spectrum m/z:804.18 (calculated value:
804.12).Theoretical elemental content (%) C48H12F4N10: C, 71.65；H, 1.50；F, 9.44；N, 17.41；Survey constituent content
(%): C, 71.71；H, 1.50；F, 9.43；N, 17.45.It is target product 18 that above-mentioned confirmation, which obtains product,.
Embodiment 15: the preparation of compound 21
Fluorenone in embodiment 13 is replaced with into structure as above, obtains compound 21.Mass spectrum m/z:928.49 (calculated value:
928.39).Theoretical elemental content (%) C60H48F4N6: C, 77.57；H, 5.21；F, 8.18；N, 9.05；Survey constituent content
(%): C, 77.61；H, 5.20；F, 8.19；N, 9.07.It is target product 21 that above-mentioned confirmation, which obtains product,.
Embodiment 16: the preparation of compound 29
Step 1: step 2 is the same as embodiment 9.
Step 3: 98% lithium hydride of 2.2 equivalents is added in the glycol dimethyl ether of 60ml, it is cooled to 0 DEG C.?
Ptfe pyridine class raw material (1.56g, 8.2mmol) is dissolved in the glycol dimethyl ether of 6ml, and is added dropwise in 1min.
Ice bath is removed, reaction solution is gradually warming up to room temperature, and reacts 15min at room temperature.Reaction solution is again cooled to 0 DEG C, by tetrachloro
The ethylene glycol dimethyl ether solution 4ml of cyclopropylene (0.712g, 4mmol) is instilled in reaction solution.Reaction solution gradually becomes kermesinus,
It is warming up to room temperature, continues stirring 44 hours.Reaction solution is poured into the ice water of 1.2L, obtained mixed liquor adjusts pH with concentrated hydrochloric acid
Be worth 1 (about addition 24ml hydrochloric acid), then extracted with 3 × 50ml ethyl acetate, merge organic phase, successively use saturated salt solution,
Deionized water, sodium bicarbonate aqueous solution washing, are finally washed with deionized primary again.Organic phase anhydrous sodium sulfate drying,
Concentration, obtains dark crude product.The crude product continues directly to react without purification.
Step 4: 98% lithium hydride of 2.2 equivalents is added in the glycol dimethyl ether of 60ml, it is cooled to 0 DEG C.?
The crude product that upper step obtains is dissolved in the glycol dimethyl ether of 6ml, and is added dropwise in 1min.Remove ice bath, reaction solution
It is gradually warming up to room temperature, and reacts 15min at room temperature.Reaction solution is again cooled to 0 DEG C, by intermediate II (4.07g,
Ethylene glycol dimethyl ether solution 4ml 15.6mmol) is instilled in reaction solution.Reaction solution gradually becomes kermesinus, is warming up to room temperature,
Continue stirring 44 hours.Reaction solution is poured into the ice water of 1.2L, obtained mixed liquor concentrated hydrochloric acid adjust pH value to 1 (about plus
Enter 24ml hydrochloric acid), it is then extracted with 3 × 50ml ethyl acetate, merges organic phase, successively use saturated salt solution, deionized water, carbon
Sour hydrogen sodium water solution washing, is finally washed with deionized primary again.Organic phase is dry with anhydrous sodium sulfate, is concentrated, and obtains depth
Color crude product.The crude product continues directly to react without purification.
Above-mentioned dark crude product is dissolved into the glacial acetic acid of 140ml, the mixed acid solution (mixed acid solution of hydrochloric acid and nitric acid is added
Prepare as follows: by 36ml, 48% dilute hydrochloric acid and 12ml, 65% concentrated nitric acid mixing, current existing system), mixed liquor continues to stir
1.5 hours, filtering, obtained orange filter cake was washed with deionized, is dried to obtain crude product, and the method for crude product distillation obtains most
Finished product (0.99g, 1.52mmol), yield 38% (on the basis of tetrachloro cyclopropylene).Mass spectrum m/z:652.15 (calculated value:
652.07).Theoretical elemental content (%) C34H8F8N6: C, 62.59；H, 1.24；F, 23.29；N, 12.88；Survey constituent content
(%): C, 62.67；H, 1.23；F, 23.32；N, 12.86.It is target product 29 that above-mentioned confirmation, which obtains product,.
Embodiment 17: the preparation of compound 32
Fluorenone in embodiment 16 is replaced with into structure as above, obtains compound 32.Mass spectrum m/z:702.13 (calculated value:
702.06).Theoretical elemental content (%) C36H6F8N8: C, 61.55；H, 0.86；F, 21.64；N, 15.95；Survey constituent content
(%): C, 61.60；H, 0.86；F, 21.63；N, 15.99.It is target product 32 that above-mentioned confirmation, which obtains product,.
Embodiment 18: the preparation of compound 34
Fluorenone in embodiment 16 is replaced with into structure as above, obtains compound 34.Mass spectrum m/z:736.27 (calculated value:
736.16).Theoretical elemental content (%) C40H20F8N6: C, 65.22；H, 2.74；F, 20.63；N, 11.41；Survey constituent content
(%): C, 65.28；H, 2.74；F, 20.65；N, 11.42.It is target product 34 that above-mentioned confirmation, which obtains product,.
Application Example 1-10
Transparent anode electrode ito substrate is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate respectively, is then existed
It is cleaned 2 minutes in plasma cleaning device, dry and is evacuated to 5 × 10-5Pa.Then by treated, ito substrate steams
Plating.Successively vapor deposition hole injection layer is material for organic electroluminescent device of the present invention (doping 5%)/25nm, vapor deposition hole passes
Defeated layer NPB/30nm, vapor deposition main body CBP: doping Ir (ppy)310% mixing/30nm, then vapor deposition electron transfer layer Alq3/
25nm, electron injecting layer LiF/0.5nm, cathode Al/200nm.
Comparative example 1
Vapor deposition hole injection layer is 2T-NATA/25nm, other steps are identical as Application Example 1-10.
It is 10mA/cm to each device measurement current density manufactured in above-mentioned Application Example 1-10 and comparative example 12When
Luminescent properties, as a result as shown in table 1 below.
Table 1
| Device | Hole injection layer | Luminous efficiency (cd/A) | Color | Driving voltage (V) |
| Comparative example | - | 35.6 | Green light | 6.6 |
| Application Example 1 | Compound 1+TM1 | 36.0 | Green light | 5.3 |
| Application Example 2 | Compound 2+TM4 | 36.2 | Green light | 5.5 |
| Application Example 3 | Compound 7+TM5 | 36.8 | Green light | 5.1 |
| Application Example 4 | Compound 8+TM7 | 35.9 | Green light | 5.2 |
| Application Example 5 | Compound 15+TM10 | 36.5 | Green light | 5.1 |
| Application Example 6 | Compound 18+TM11 | 36.7 | Green light | 5.2 |
| Application Example 7 | Compound 21+TM19 | 37.8 | Green light | 4.9 |
| Application Example 8 | Compound 29+TM22 | 36.0 | Green light | 5.3 |
| Application Example 9 | Compound 32+TM7 | 36.6 | Green light | 5.1 |
| Application Example 10 | Compound 34+TM19 | 37.7 | Green light | 5.0 |
The above result shows that material of the invention is applied in organic electroluminescence device, luminous efficiency is high, driving voltage
It is low, it is luminous organic material of good performance.
Obviously, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should refer to
It out, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field
Bright some improvement and modification can also be carried out, these improvement and modification are also fallen within the scope of the present invention.
Claims (10)
1. a kind of material for organic electroluminescent device, which is characterized in that including material of main part and dopant material, the main body material
Material has structure shown in formula (I):
Wherein, Ar1、Ar2The independent aryl for being 6~25 selected from carbon atom number；R1、R2、R3、R4、R5It is independent to be selected from hydrogen, deuterium, carbon
The alkyl that atomicity is 1~4；X is independent to be selected from hydrogen, cyano or trifluoromethyl；
The dopant material has structure shown in formula (II):
Wherein, R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl, substituted or unsubstituted C6~C30 aryl,
The heteroaryl of substituted or unsubstituted C3~C30 orOne of or R6With R7、R8With R9、R10With R11
Between independently condense cyclization；
R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, the alkyl of C1~C10, substituted or unsubstituted C6
One of the aryl of~C30, heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer；
R12~R14Independently selected from one of halogen, nitro, cyano or trifluoromethyl.
2. material for organic electroluminescent device according to claim 1, which is characterized in that material of main part shown in formula (I)
In, Ar1、Ar2It is independent to be selected from phenyl, terphenyl, fluorenyl, Spirofluorene-based or fluoranthene base.
3. material for organic electroluminescent device according to claim 1, which is characterized in that material of main part shown in formula (I)
In, R1、R2、R3、R4、R5It is independent to be selected from hydrogen, deuterium, the alkyl that carbon atom number is 1~4.
4. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R6~R11Independently selected from halogen, nitro, cyano, trifluoromethyl, substituted or unsubstituted phenyl, substituted or unsubstituted
Pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted triazine radical orOne of, wherein
R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, the alkyl of C1~C10, substituted or unsubstituted C6~
One of the aryl of C30, heteroaryl of substituted or unsubstituted C3~C30；
M, n independently selected from 0 to 4 integer.
5. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R6~R11Independently selected from cyano, trifluoromethyl orOne of, wherein R15、R16Independently selected from
Hydrogen, halogen, nitro, cyano, trifluoromethyl, the alkyl of C1~C4, substituted or unsubstituted C6~C30 aryl, replace or not
One of substituted heteroaryl of C3~C30；
M, n independently selected from 0 to 4 integer.
6. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R15、R16Independently selected from hydrogen, halogen, nitro, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, connection
Phenyl or pyridyl group.
7. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R6~R11Independently selected from any one of cyano, trifluoromethyl or structure as follows:
8. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R6、R8、R10In at least one be cyano or trifluoromethyl.
9. material for organic electroluminescent device according to claim 1, which is characterized in that dopant material shown in formula (II)
In, R6With R7、R8With R9、R10With R11Between be independently fused into substituted or unsubstituted pyridine.
10. a kind of organic electroluminescence device, including anode, cathode and one layer between the anode and the cathode
Above organic matter layer, which is characterized in that at least one layer in described one layer or more of organic matter layer includes claim 1~9
Described in any item material for organic electroluminescent device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3930023A1 (en) * | 2020-06-22 | 2021-12-29 | Novaled GmbH | Organic electronic device comprising a compound of formula (1), display device comprising the organic electronic device as well as compounds of formula (1) for use in organic electronic devices |
| EP4199132A1 (en) * | 2021-12-20 | 2023-06-21 | Novaled GmbH | Charge generation layer comprising a compound of formula (i), organic electronic device and display device comprising the charge generation layer as well as compounds of formula (i) |
-
2018
- 2018-11-13 CN CN201811343598.9A patent/CN109485576A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3930023A1 (en) * | 2020-06-22 | 2021-12-29 | Novaled GmbH | Organic electronic device comprising a compound of formula (1), display device comprising the organic electronic device as well as compounds of formula (1) for use in organic electronic devices |
| EP4199132A1 (en) * | 2021-12-20 | 2023-06-21 | Novaled GmbH | Charge generation layer comprising a compound of formula (i), organic electronic device and display device comprising the charge generation layer as well as compounds of formula (i) |
| WO2023117749A1 (en) * | 2021-12-20 | 2023-06-29 | Novaled Gmbh | Charge generation layer comprising a compound of formula (i), organic electronic device and display device comprising the charge generation layer as well as compounds of formula (i) |
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