CN109942541A - A kind of fluorenes and carbazole derivates and its preparation method and application - Google Patents
A kind of fluorenes and carbazole derivates and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic synthesis sciemtifec and technical spheres, and in particular to a kind of fluorenes simultaneously carbazole derivates and its application.Fluorenes provided by the present invention and carbazole derivates are that simultaneously carbazole unit bridge joint volume is biggish by the substituted or unsubstituted arylamine of alkyl or aryl phosphorus-oxygen groups to specific fluorenes, the hole mobile material and improved efficiency layer material of the high comprehensive performances such as a based electroluminescent, thermal stability and the service life formed, are able to satisfy requirement of the industrialization level to device overall performance.
Description
Technical field
The invention belongs to organic synthesis sciemtifec and technical spheres, and in particular to a kind of fluorenes and carbazole derivates and preparation method thereof and answer
With.
Background technique
Carbazole is the nitrogen-containing heterocycle compound of electron rich, and the electrophilic nitrogen-atoms of carbazole absorbs on carbon-carbon double bond through inductive effect
Electronics, while having the pi-conjugated effect of P- again, therefore, carbazole ring has very high hole mobility and luminous efficiency, makes its derivative
There is potential be widely applied in fields such as photoelectric material, dyestuff, medicine, Supramolecular Recognitions.
Due to being limited by molecular structure, single carbazole compound molecule thermal stability is poor, simultaneously as in solid phase
Light red shift occurs or is emitted so as to cause fluorescent quenching for small molecule emitter material reunion easy to form.Therefore, current many scholars
By carbazole ring design at the condensed cyclic structure of similar pentacene, to increase plane rigid structure, and further by being easy to repair
Triazine, carbazole, the groups such as arylamine are introduced on 9 atoms of decorations to reduce molecule and reunite quenching, improve its in current efficiency, shine
Efficiency, photochromic, in terms of brightness performance, also have made some progress in this field at present, however, the electroluminescent hair of carbazoles macromolecule
Luminescent material and device still have some problems, usually while optimizing some indexs, cause other performance to be deteriorated, Wu Fada
To commercial applications level, such as: the compound of design has very high hole transport rate, but exists between electron transfer rate
Huge transmission rate difference causes carrier electrons-hole uneven, causes a degree of non-spoke by carrier traps
Penetrate transition；Material layer a degree of knot when the widened rigid planar structure of material causes evaporation film-forming and device work to overheat
Crystallization.Therefore the fine structure of molecule must be designed, from luminescence mechanism to optimize the performance indexes of material.
In addition, three-dimensional effect has tremendous influence to the synthesis of compound, carbazole 3,6- are activated by nitrogen-atoms, Duo Zhongqin
Electric substitution reaction is all prone in the two positions, and therefore, 3,6, No. 9 positions of carbazole ring are easy to introduce it by chemical modification
His functional group, and 1,2,7,8 synthesis replaced in carbazole is much more difficult, constraining the more excellent carbazoles of performance has
The development of electroluminescent material.
Summary of the invention
To solve the deficiencies in the prior art, one aspect of the present invention provides a kind of fluorenes and carbazole derivates, general structure
As shown in following formula (I):
Wherein, n is 0 or 1；
Any one X1For C, other X1Independent is CH, CR0Or N；
Any one X2For C, other X2Independent is CH, CR0Or N；
Y is N or P=O；
R1、R2It is independently C6~45Aryl or C3~45Heteroaryl, R1With R2It is identical or different；
The R0Selected from cyano, nitro, C1~20Alkyl, C1~20Alkoxy, C1~20Alkylthio group, C6~45Fragrant oxygen
Base, C6~45Arylthio.
Specifically, the R1Or R2C6~45Aryl be selected from: by C1~20The substituted or unsubstituted phenyl of alkyl, by
C1~20The substituted or unsubstituted xenyl of alkyl, by C1~20The substituted or unsubstituted phenyl napthyl of alkyl, by C1~20Alkane
The substituted or unsubstituted naphthalene of base, by C1~20The substituted or unsubstituted naphthylphenyl of alkyl, by C1~20Alkyl replace or not
Substituted anthryl, by C1~20The substituted or unsubstituted fluorenyl of alkyl；
Specifically, the R1Or R2C3~45Heteroaryl be selected from: by C1~20The substituted or unsubstituted benzofuran of alkyl
Base, by C1~20The substituted or unsubstituted benzothienyl of alkyl, by C1~20The substituted or unsubstituted dibenzofurans of alkyl
Base, by C1~20The substituted or unsubstituted dibenzothiophene of alkyl, by C1~20The substituted or unsubstituted carbazyl of alkyl, by
C1~20The substituted or unsubstituted phenyl carbazole base of alkyl, by C1~20The substituted or unsubstituted carbazyl phenyl of alkyl.
Preferably, X1Number for N is 0-3, X2Number for N is 0~3, n 1.
Preferably, simultaneously carbazole derivates include chemical formula 1-152 compound represented to the fluorenes:
The present invention also provides the preparation methods of fluorenes and carbazole derivates, include the following steps:
S1. by formula (a) compound represented and formula (b) compound represented investment reactor, the first palladium is then put into
Catalyst, the first Phosphine ligands, the first base reagent and the first solvent, ultrasound remove air, react under nitrogen protection, obtain formula
(c) compound shown in；
S2. formula (c) compound represented is put into reactor, then puts into the second palladium catalyst, the second Phosphine ligands, the
Two base reagents and the second solvent, ultrasound remove air, react under nitrogen protection, obtain compound shown in formula (d)；
S3. by formula (d) compound represented and formula (e) compound represented investment reactor, third copper is then put into
Catalyst, cocatalyst, third base reagent and third solvent, ultrasound remove air, react under nitrogen protection, obtain formula
(f) compound shown in；
S4. by the investment reactor of compound shown in formula (f) and formula (g), then the 4th palladium catalyst is put into, tetraphosphine is matched
Body, the 4th base reagent and the 4th solvent, ultrasound remove air, and reaction obtains the fluorenes and carbazole derivates under nitrogen protection；
Wherein, Z1、Z2、Z3、Z4It is independently selected from Cl, Br, I.
Specifically, formula (a) compound represented described in step S1, formula (b) compound represented, the first palladium catalyst,
The feed ratio of first Phosphine ligands, the first base reagent and the first solvent is 1mmol:0.5~1.5mmol:0.005~0.02mmol:
0.005~0.02mmol:2~4mmol:3~15mL, reaction temperature are 60~80 DEG C, and liquid phase monitors formula (a) compound represented
Reaction is completed, and compound shown in formula (c) can be obtained in quenching reaction, processing；
Step S2 Chinese style (c) compound represented, the second palladium catalyst, the second Phosphine ligands, the second base reagent and second are molten
The feed ratio of agent is 1mmol:0.02~0.2mmol:0.01~0.3mmol:2~5mmol:2~10mL, reaction temperature 100
~165 DEG C, liquid phase monitors the reaction of formula (c) compound represented and completes, and restores room temperature, and chemical combination shown in formula (d) can be obtained in processing
Object；
Step S3 Chinese style (d) compound represented, formula (e) compound represented, third copper catalyst, cocatalyst,
The feed ratio of third base reagent and third solvent be 1mmol:1.1~3mmol:0.1~0.5mmol:0.1~0.5mmol:2~
5mmol:2~10mL, reaction temperature are 100~165 DEG C, and liquid phase monitors the reaction of formula (d) compound represented and completes, recovery room
Temperature, processing, can be obtained compound shown in formula (f)；
Compound shown in formula (f) described in step S4, compound shown in formula (g), the 4th palladium catalyst, the 4th Phosphine ligands,
The feed ratio of 4th base reagent and the 4th solvent is 1:1~3:0.005~0.02mmol:0.01~0.04mmol:2~4mmol:
2~10mL, reaction temperature are 90~115 DEG C, and liquid phase monitors the reaction of formula (f) compound represented and completes, recovery room temperature, processing,
The fluorenes and carbazole derivates of target can be obtained.
Specifically, first palladium catalyst is tris(dibenzylideneacetone) dipalladium, first Phosphine ligands are triphenyl
Phosphine, first base reagent are sodium tert-butoxide, and first solvent is that second alcohol and water is mixed according to what the volume ratio of 2:1 was mixed to get
Close solution, second palladium catalyst be palladium acetate, second Phosphine ligands be tri-tert-butylphosphine tetrafluoroborate, described second
Base reagent is potassium carbonate, and second solvent is N-Methyl pyrrolidone, and the third copper catalyst is cuprous iodide, described auxiliary
Crown ether -6 co-catalyst 18-, the third base reagent be potassium carbonate, the third solvent be dimethyl acetamide, the described 4th
Palladium catalyst is tris(dibenzylideneacetone) dipalladium, the 4th Phosphine ligands be tri-tert-butylphosphine tetrafluoroborate, the described 4th
Base reagent is sodium tert-butoxide, and the 4th solvent is toluene.
The present invention also provides the application of above-mentioned fluorenes and carbazole derivates in preparation display device.
The present invention also provides a kind of organic electroluminescence devices, are made of a pair of electrodes and interelectrode organic layer,
The organic layer includes at least hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, the sky
Cave transport layer and/or luminescent layer include above-mentioned fluorenes and carbazole derivates.
Specifically, the organic layer includes at least hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electricity
Sub- implanted layer, and close to the improved efficiency layer of the side of luminescent layer in organic layer, the improved efficiency layer includes above-mentioned
Fluorenes and carbazole derivates.
The present invention gives full play to the characteristics of rigid plane biphenyl structural wide energy gap, by by the 1 of 9H- carbazole, 2 and 9,9-
3,4 of dimethyl -9H- fluorenes are thick and form the fluorenes and carbazole unit of a kind of distortion, then lead on the nitrogen site that it is easy to modify
There is the biphenyl structural bridge joint for crossing azepine or non-azepine large volume of branched chain compound to form a kind of novel electroluminescent hair of synthesis
The excellent fluorenes of light characteristic and carbazole derivates.
Relative to the thick of other functional groups with rigid plane biphenyl structural and and other sites thick and, 9H- click
The 1 of azoles, 2 thick and form interior torsion rigidity nonplanar structure with 3,4 of 9,9- dimethyl -9H- fluorenes, and 9 of carbazole push away
The cloud density for the conjugated structure that electron group extends 1,2 is effectively adjusted, and configuration is close, assigns group itself more
High thermal stability and electroluminescent characteristic, in addition, the double methyl structurals of 9 of fluorenes avoid the building-up effect of intermolecular material, this hair
Bright fluorenes and carbazole unit improve thermal stability and the service life of material from intramolecule structure and accumulation mode.
Based on above-mentioned fluorenes and carbazole structure unit, the present invention by doping or non-mixes on the nitrogen site that it is easy to modify
Miscellaneous biphenyl structural bridge joint volume is biggish by the substituted or unsubstituted arylamine of alkyl or aryl phosphorus-oxygen groups, forms a kind of comprehensive
Close the fluorenes and carbazole derivates of function admirable.On the one hand, simultaneously carbazole structure unit passes through doped or non-doped biphenyl to above-mentioned fluorenes
Structure bridges arylamine or aryl phosphorus-oxygen groups, its nonplanar conjugated structure of further expansion makes it have excellent hole
Transmission characteristic；On the other hand, the branched structure and tool of introducing being had by the substituted or unsubstituted arylamine of alkyl or phosphorus-oxygen groups
There is the fluorenes of branched structure and carbazole structure unit complements each other, further improves the amorphism of fluorenes and carbazole derivates, compared with
Long biphenyl chain makes the biggish structural unit of volume separate arrangement in steric configuration again, avoids the aggregation inducing effect of material
It answers, effectively avoids cracking and crystallinity problem of the existing electroluminescent organic material in vapor deposition and device use, be one
The excellent hole mobile material of kind.Particularly, the nitrogen-atoms for pushing away characteristic electron is doped in the biphenyl structural of bridging, into one
Step reduces the lowest energy level of material, imparts material with better hole transport and exciton barrier properties, can be further by light
It is limited in luminescent layer, improves hole-electron in the combined efficiency of luminescent layer, be a kind of excellent improved efficiency layer material,
It has a good application prospect in organic electroluminescence device.
Detailed description of the invention
Fig. 1 is that compound provided by the present invention (26) are used as hole transmission layer or the device energy as improved efficiency layer
Grade figure；
Fig. 2 is wavelength-luminous intensity performance diagram of device 6 of the invention, device 19 and device 20.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
It limits the scope of the invention.
Embodiment 1: the synthesis of intermediate fluorenes and carbazole
S1. in the there-necked flask of 250mL, bromo- 9, the 9- dimethyl -9H- fluorenes (8.20g, 30mmol) of investment 4-, 2- chloroaniline
(4.59g, 36mmol), triphenylphosphine (0.04g, 0.15mmol), sodium tert-butoxide (8.65g, 90mmol), be added 80mL ethyl alcohol and
40mL water is added tris(dibenzylideneacetone) dipalladium (0.27g, 0.3mmol) under nitrogen atmosphere, reacts 1-4h, liquid at 70 DEG C
Mutually bromo- 9, the 9- dimethyl -9H- fluorenes reaction of monitoring 4- is completed, and water quenching reaction, liquid separation, organic phase concentration, with petroleum ether mistake is added
Silicagel column elution, leacheate concentration, can be obtained N- (2- chlorphenyl) -9,9- dimethyl -9H- fluorenes -4- of colorless and transparent oily
Amine 9.02g, yield 94%, purity 99.85%.
S2. in the there-necked flask of 100mL, above-mentioned N- (2- chlorphenyl) -9,9- dimethyl -9H- fluorenes -4- amine is put into
(5.67g, 20mmol), tri-tert-butylphosphine tetrafluoroborate (0.06g, 0.2mmol), potassium carbonate (11.05g, 80mmol) are added
40mLN- methyl pyrrolidone is added palladium acetate (0.09g, 0.4mmol) under nitrogen atmosphere, reacts 1-4h, liquid at 160 DEG C
Mutually monitoring reaction is completed, and is cooled to room temperature, and is washed, liquid separation, organic phase concentration, crosses silicagel column elution with petroleum ether, leacheate is dense
The fluorenes and carbazole 5.04g of yellow powder, yield 89%, purity 99.32% can be obtained in contracting.
Embodiment 2: the synthesis of compound (4)
S3. in the there-necked flask of 250mL, above-mentioned fluorenes and carbazole (4.25g, 15mmol), the bromo- 2- iodine pyridine of 5- are put into
75mL dimethyl second is added in (5.67g, 20mmol), 18- crown ether -6 (0.79g, 3mmol), potassium carbonate (10.36g, 75mmol)
Amide is added cuprous iodide (0.57g, 3mmol) under nitrogen atmosphere, and 4-8h is reacted at 160 DEG C, and liquid phase monitoring reaction is completed,
It is cooled to room temperature, washes, filtering, filter cake is with ethyl acetate hot beating one time of 3-5 times, then with the ethyl acetate of 10:1: ethyl alcohol
Mixed solvent hot beating one time, intermediate 12- (5- bromopyridine -2- the base)-fluorenes and carbazole of white powder can be obtained
5.47g, yield 83%.
S4. in the there-necked flask of 100mL, put into above-mentioned intermediate 12- (5- bromopyridine -2- base)-fluorenes and carbazole (2.20g,
5mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol), tri-tert-butylphosphine tetrafluoroborate (0.06g, 0.2mmol), tertiary fourth
50mL toluene is added in sodium alkoxide (0.96g, 10mmol), under nitrogen atmosphere, addition tris(dibenzylideneacetone) dipalladium (0.09g,
0.1mmol), 4-8h is reacted at 110 DEG C, liquid phase monitors 12- (5- bromopyridine -2- base)-fluorenes and carbazole reaction is completed, and is cooled to room
Temperature is washed, filtering, filter cake ethyl alcohol: ethyl acetate is twice of solvent hot beating of 5:1, and the change of white powder can be obtained
Close object (4) 2.50g, yield 90%.
Mass spectrograph MALDI-TOF-MS (m/z)=555.7243, theoretical molecular weight: 555.7250；Anal.Calcd for
C40H33N3(%): C 86.45, H 5.99, N 7.56, Found:C 86.45, H 6.00, N 7.55.
Embodiment 3: the synthesis of compound (9)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 4-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with diphenylamines (1.52g, 9mmol), other conjunctions
At process with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio, reaction condition are identical)
It can be obtained, compound (9) 2.50g of white powder, yield 90% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=602.7803, theoretical molecular weight: 602.7810；Anal.Calcd for
C45H34N2(%): C 89.67, H 5.69, N 4.65, Found:C 89.69, H 5.68, N 4.64.
Embodiment 4: the synthesis of compound (10)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 4-
(7.18g, 20mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants,
Molar ratio, reaction condition are identical) compound (10) 2.74g of white powder, yield 87% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=630.8356, theoretical molecular weight: 630.8350；Anal.Calcd for
C47H38N2(%): C 89.49, H 6.07, N 4.44, Found:C 89.51, H 6.06, N 4.43.
Embodiment 5: the synthesis of compound (13)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 3'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with diphenylamines (1.52g, 9mmol), other conjunctions
At process with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio, reaction condition are identical)
Compound (13) 2.67g of white powder, yield 89% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=602.7802, theoretical molecular weight: 602.7810；Anal.Calcd for
C45H34N2(%): C 89.67, H 5.69, N 4.65, Found:C 89.64, H 5.70, N 4.66.
Embodiment 6: the synthesis of compound (19)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with 4,4- isopropyl diphenyl amine (2.28g,
9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio,
Reaction condition is identical) compound (19) 2.94g of white powder, yield 86% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=686.9430, theoretical molecular weight: 686.9430；Anal.Calcd for
C51H46N2(%): C 89.17, H 6.75, N 4.08, Found:C 89.15, H 6.75, N 4.10.
Embodiment 7: the synthesis of compound (24)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 3- of 4'-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with 4,4- tert-butyl diphenylamine (2.53g,
9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio,
Reaction condition is identical) compound (24) 2.98g of white powder, yield 83% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=714.9967, theoretical molecular weight: 714.9970；Anal.Calcd for
C53H50N2(%): C 89.03, H 7.05, N 3.92, Found:C 89.06, H 7.04, N 3.90.
Embodiment 8: the synthesis of the bromo- 2- of intermediate 5- (4- iodophenyl) pyridine
In the there-necked flask of 250mL, Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol), 5- bromopyridine -2- boric acid are put into
(6.05g, 30mmol), potassium carbonate (8.29g, 60mmol), is added 100mL tetrahydrofuran and 50mL water adds under nitrogen atmosphere
Enter tetrakis triphenylphosphine palladium (2.31g, 2mmol), 2-8h is reacted at 110 DEG C, it is complete that liquid phase monitors 5- bromopyridine -2- acid reaction
At being cooled to room temperature, wash, filtering, the bromo- 2- of intermediate 5- (4- iodophenyl) can be obtained with twice of ethyl alcohol hot beating in filter cake
Pyridine 10.25g, yield 95%.
Embodiment 9: the synthesis of compound (26)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into 5- bromo- 2- (the 4- iodine in embodiment 8
Phenyl) pyridine (7.20g, 20mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but its
His reactant, molar ratio, reaction condition are identical) compound (26) 2.68g of white powder, yield 85% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=631.8230, theoretical molecular weight: 631.8230；Anal.Calcd for
C46H37N3(%): C 87.45, H 5.90, N 6.65, Found:C 87.46, H 5.90, N 6.65.
Embodiment 10: the synthesis of intermediate 3- (3- bromophenyl) -5- iodine pyridine
By Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol) in embodiment 8 replace with 3,5- diiodopyridine (11.58g,
35mmol), 5- bromopyridine -2- boric acid (6.05g, 30mmol) replaces with 3- bromobenzeneboronic acid (6.02g, 30mmol), other synthesis
3- (3- bromophenyl) -5- iodine pyridine 10.15g, yield 94% can be obtained with embodiment 8 in process.
Embodiment 11: the synthesis of compound (36)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into 3- (the 3- bromobenzene in embodiment 10
Base) -5- iodine pyridine (7.20g, 20mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different,
But other reactants, molar ratio, reaction condition are identical) compound (36) 3.08g of white powder, yield can be obtained
86%.
Mass spectrograph MALDI-TOF-MS (m/z)=715.9847, theoretical molecular weight: 715.9850；Anal.Calcd for
C52H49N3(%): C 87.23, H 6.90, N 5.87, Found:C 87.25, H 6.90, N 5.84.
Embodiment 12: the synthesis of compound (46)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 4-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- (4- tolyl)-[1,1'- biphenyl] -4-
Amine (2.33g, 9mmol), (intermediate of each corresponding step can be different, but other are reacted with embodiment 2 for other synthesis processes
Object, molar ratio, reaction condition are identical) compound (46) 2.92g of white powder, yield 84% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=692.9051, theoretical molecular weight: 692.9060；Anal.Calcd for
C52H40N2(%): C 90.14, H 5.82, N 4.04, Found:C 90.16, H 5.81, N 4.05.
Embodiment 13: the synthesis of compound (52)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- (4- tert-butyl-phenyl)-[1,1'- connection
Benzene] -4- amine (2.71g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other
Reactant, molar ratio, reaction condition are identical) compound (52) 3.00g of white powder, yield 82% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=734.9875, theoretical molecular weight: 734.9870；Anal.Calcd for
C55H46N2(%): C 89.88, H 6.31, N 3.81, Found:C 89.88, H 6.30, N 3.82.
Embodiment 14: the synthesis of compound (53)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 3- of 4'-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- phenyl-[1,1'- biphenyl] -3- amine
(2.21g, 9mmol), other synthesis processes with embodiment 2 (per the corresponding step body in centre one can be different, but other reactants,
Molar ratio, reaction condition are identical) compound (53) 2.88g of white powder, yield 85% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=678.8794, theoretical molecular weight: 678.8790；Anal.Calcd for
C51H38N2(%): C 90.23, H 5.64, N 4.13, Found:C 90.21, H 5.64, N 4.16.
Embodiment 15: the synthesis of the bromo- 2- of intermediate 5- (4- iodophenyl) pyridine
By Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol) in embodiment 8 replace with 2,5- diiodopyridine (11.58g,
35mmol), 5- bromopyridine -2- boric acid (6.05g, 30mmol) replaces with 4- bromobenzeneboronic acid (6.02g, 30mmol), other synthesis
2- (4- bromophenyl) -5- iodine pyridine 9.72g, yield 90% can be obtained with embodiment 8 in process.
Embodiment 16: the synthesis of compound (61)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into 2- (the 4- bromobenzene in embodiment 15
Base) -5- iodine pyridine (7.20g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- phenyl -, and [1,1'- joins
Benzene] -4- amine (2.21g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other
Reactant, molar ratio, reaction condition are identical) compound (61) 2.92g of white powder, yield 86% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=679.8666, theoretical molecular weight: 679.8670；Anal.Calcd for
C50H37N3(%): C 88.33, H 5.49, N 6.18, Found:C 88.31, H 5.50, N 6.19.
Embodiment 17: the synthesis of the bromo- 2- of intermediate 5- (3- iodophenyl) pyridine
By Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol) in embodiment 8 replace with 1,3- diiodo-benzene (11.55g,
35mmol), 5- bromopyridine -2- boric acid (6.05g, 30mmol) replaces with (5- bromopyridine -2- base) boric acid (6.05g, 30mmol),
The bromo- 2- of 5- (3- iodophenyl) pyridine 10.25g, yield 95% can be obtained with embodiment 8 in other synthesis processes.
Embodiment 18: the synthesis of compound (70)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into the bromo- 2- (3- of the 5- in embodiment 17
Iodophenyl) pyridine (7.20g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- (4- tolyl)-[1,
1'- biphenyl] -4- amine (2.33g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different,
But other reactants, molar ratio, reaction condition are identical), compound (70) 2.90g of white powder, yield can be obtained
84%.
Mass spectrograph MALDI-TOF-MS (m/z)=693.8937, theoretical molecular weight: 693.8940；Anal.Calcd for
C51H39N3(%): C 88.28, H 5.67, N 6.06, Found:C 88.29, H 5.65, N 6.06.
Embodiment 19: the synthesis of the bromo- 2- of intermediate 4- (3- iodophenyl) pyridine
By Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol) in embodiment 8 replace with 1,3- diiodo-benzene (11.55g,
35mmol), 5- bromopyridine -2- boric acid (6.05g, 30mmol) replaces with (4- bromopyridine -2- base) boric acid (6.05g, 30mmol),
The bromo- 2- of 4- (3- iodophenyl) pyridine 10.04g, yield 93% can be obtained with embodiment 8 in other synthesis processes.
Embodiment 20: the synthesis of compound (75)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into the bromo- 2- (3- of the 4- in embodiment 18
Iodophenyl) pyridine (7.20g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with N- (4- cumene
Base)-[1,1'- biphenyl] -3- amine (2.59g, 9mmol), other synthesis processes are the same as (the intermediate of each corresponding step of embodiment 2
Can be different, but other reactants, molar ratio, reaction condition are identical), compound (75) 2.96g of white powder can be obtained,
Yield 82%.
Mass spectrograph MALDI-TOF-MS (m/z)=721.9483, theoretical molecular weight: 721.9480；Anal.Calcd for
C53H43N3(%): C 88.18, H 6.00, N 5.82, Found:C 88.19, H 6.00, N 5.81.
Embodiment 21: the synthesis of compound (85)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 4-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with diphenyl phosphorus oxygen (1.82g, 9mmol),
(intermediate of each corresponding step can be different, but other reactants, molar ratio, reaction condition phase with embodiment 2 for his synthesis process
Together), compound (85) 2.78g of white powder, yield 87% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=635.7463, theoretical molecular weight: 635.7468；Anal.Calcd for
C45H34N (%): C 85.02, H 5.39, N 2.20, Found:C 85.00, H 5.40, N 2.22.
Embodiment 22: the synthesis of compound (90)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 3'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with di-p-tolyl phosphorus oxygen (2.07g,
9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio,
Reaction condition is identical), compound (90) 2.83g of white powder, yield 85% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=663.8008, theoretical molecular weight: 663.8008；Anal.Calcd for
C47H38N (%): C 85.04, H 5.77, N 2.11, Found:C 85.05, H 5.76, N 2.09.
Embodiment 23: the synthesis of compound (96)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with two pairs of tert-butyl-phenyl phosphorus oxygens (2.83g,
9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants, molar ratio,
Reaction condition is identical), compound (96) 3.15g of white powder, yield 84% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=747.9622, theoretical molecular weight: 747.9628；Anal.Calcd for
C53H50N (%): C 85.11, H 6.74, N 1.87, Found:C 85.10, H 6.75, N 1.86.
Embodiment 24: the synthesis of compound (102)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into 5- bromo- 2- (the 4- iodine in embodiment 8
Phenyl) pyridine (7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with two p-methylphenyl phosphorus oxygens
(2.07g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants,
Molar ratio, reaction condition are identical), compound (102) 2.86g of white powder, yield 86% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=664.7892, theoretical molecular weight: 664.7888；Anal.Calcd for
C46H37N2(%): C 83.11, H 5.61, N 4.21, Found:C 83.10, H 5.60, N 4.22.
Embodiment 25: the synthesis of compound (117)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into the bromo- 2- (3- of the 5- in embodiment 17
Iodophenyl) pyridine (7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with diphenyl phosphorus oxygen
(1.82g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants,
Molar ratio, reaction condition are identical), compound (117) 2.73g of white powder, yield 86% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=636.7354, theoretical molecular weight: 636.7348；Anal.Calcd for
C44H33N2(%): C 83.00, H 5.22, N 4.40, Found:C 83.00, H 5.22, N 4.40.
Embodiment 26: the synthesis of compound (121)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 4'- of 4-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with [1,1'- biphenyl] -4- base (phenyl) phosphorus oxygen
(2.50g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants,
Molar ratio, reaction condition are identical), compound (121) 2.95g of white powder, yield 83% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=711.8440, theoretical molecular weight: 711.8448；Anal.Calcd for
C51H38N (%): C 86.05, H 5.38, N 1.97, Found:C 86.07, H 5.38, N 1.95.
Embodiment 27: the synthesis of compound (134)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into iodo- 1, the 1'- biphenyl of the bromo- 3'- of 3-
(7.18g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with [1,1'- biphenyl] -4- base (phenyl) phosphorus oxygen
(2.63g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but other reactants,
Molar ratio, reaction condition are identical), compound (134) 2.98g of white powder, yield 82% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=725.8724, theoretical molecular weight: 725.8718；Anal.Calcd for
C52H40N (%): C 86.04, H 5.55, N 1.93, Found:C 86.06, H 5.53, N 1.94.
Embodiment 28: the synthesis of compound (140)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into 5- bromo- 2- (the 4- iodine in embodiment 8
Phenyl) pyridine (7.20g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with [1,1'- biphenyl] -4- base
(4- tert-butyl-phenyl) phosphorus oxygen (3.00g, 9mmol), (intermediate of each corresponding step can with embodiment 2 for other synthesis processes
Difference, but other reactants, molar ratio, reaction condition are identical), compound (140) 2.98g of white powder can be obtained,
Yield 82%.
Mass spectrograph MALDI-TOF-MS (m/z)=768.9416, theoretical molecular weight: 768.9408；Anal.Calcd for
C54H45N2(%): C 84.35, H 5.90, N 3.64, Found:C 84.36, H 5.88, N 3.64.
Embodiment 29: the synthesis of the bromo- 5- of intermediate 3- (3- iodophenyl) pyridine
By Isosorbide-5-Nitrae-diiodo-benzene (11.55g, 35mmol) in embodiment 8 replace with 1,3- diiodo-benzene (11.55g,
35mmol), 5- bromopyridine -2- boric acid (6.05g, 30mmol) replaces with (5- bromopyridine -3- base) boric acid (6.05g, 30mmol),
The bromo- 5- of 3- (3- iodophenyl) pyridine 10.24g, yield 95% can be obtained with embodiment 8 in other synthesis processes.
Embodiment 30: the synthesis of compound (150)
The bromo- 2- iodine pyridine (5.67g, 20mmol) of 5- in embodiment 2 is replaced with into the bromo- 5- (3- of the 3- in embodiment 27
Iodophenyl) pyridine (7.20g, 20mmol), 4,4- dimethyl diphenylamines (1.78g, 9mmol) replace with [1,1'- biphenyl] -4- base
(phenyl) phosphorus oxygen (2.63g, 9mmol), other synthesis processes with embodiment 2 (intermediate of each corresponding step can be different, but its
His reactant, molar ratio, reaction condition are identical), compound (150) 2.98g of white powder, yield 82% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=726.8595, theoretical molecular weight: 726.8598；Anal.Calcd for
C51H39N2(%): C 84.27, H 5.41, N 3.85, Found:C 84.25, H 5.40, N 3.87.
Embodiment 31: the preparation of electronic component
By tin indium oxide (ITO) glass substrate in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, Zhi Houxian
Continued to be cleaned by ultrasonic 15min with acetone and isopropanol afterwards, be dried in vacuo 2h (105 DEG C), at the UV ozone of followed by 15min
Reason, is sent to vacuum evaporation plating machine for ito glass substrate.
By 4,4', 4-three [N- (naphthalene-2- base)-N- phenyl-amino)] triphenylamine (2T-NATA) vacuum depositions are in ito glass
Substrate forms hole injection layer up to the thickness of 10nm.
By N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines (NPB) vacuum deposition is infused in hole
The thickness for entering layer up to 60nm forms hole transmission layer.
By 3- tert-butyl -9,10- two (2- naphthalene) anthracene (MADN) (as luminescent layer material of main part) and 2- ethyl-N- (4-
((E) -4- ((E) -4- ((2- ethyl -6- methylbenzene) (phenyl) amine) vinyl) vinyl) phenyl) -5- methyl N-aniline
(BUBD-1) (as luminescent layer guest materials) with the common vacuum deposition of the weight ratio of 94:6 on the hole transport layer to 12nm's
Thickness forms luminescent layer.
By 3,3'- [5'- [3- (3- pyridyl group) phenyl] [1,1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines
(TmPyPB) vacuum deposition forms electron transport layer materials to the thickness of 15nm on the light-emitting layer.
Lithium fluoride (LiF) vacuum deposition is formed into electron injecting layer to the thickness of 1nm on the electron transport layer.
By weight ratio be 90:10 magnesium (Mg) and silver (Al) vacuum deposition in electron injecting layer up to the thickness shape of 100nm
At cathode.
Specific structure is as follows: ITO/2T-NATA (10nm)/NPB (60nm)/MADN:6%wt BUBD-1 (12nm)/
TmPyPB(15nm)/LiF(1nm)/Mg:Al(100nm)
Embodiment 2~5, embodiment 7, embodiment 9, embodiment 11~12, embodiment 14, embodiment 18, reality is respectively adopted
It applies example 21~27, the compound that embodiment 30 is prepared and control compounds 1 and substitutes above-mentioned NPB, to complete Organic Electricity
The preparation of electroluminescence device.Apply forward bias direct current on the organic electroluminescence device of preparation to its characteristics of luminescence, heat
Stability and service life are detected, and specific detection data is shown in Table 1:
1 electronic component performance of table characterization
Testing result shows using fluorenes provided by the invention and carbazole derivates are prepared as hole mobile material
Organic electroluminescence device start voltage, brightness, current efficiency, coloration, glass transition temperature and in terms of have
Excellent performance, and NPB in the prior art and the comparison 1 with approximate construction are significantly better than as hole transmission layer preparation
Device.
It respectively will be using embodiment 3~5, embodiment 7, embodiment 9, embodiment 12, embodiment 14, embodiment 16, implementation
The compound and 1 vacuum of comparison that example 18, embodiment 21~22, embodiment 24, embodiment 27, embodiment 30 are prepared are heavy
Product improves layer material to the thickness formation efficiency of 20nm on the hole transport layer, to complete the system of organic electroluminescence device
It is standby.Performance detection is carried out to the organic electroluminescence device of preparation, specific detection data is shown in Table 2:
2 electronic component performance of table characterization
Wherein Fig. 1 is that compound (26) are used as hole transmission layer or the device energy diagram as improved efficiency layer, Fig. 2 are
The wavelength of device 6, device 19 and device 20-luminous intensity performance diagram.
Testing result shows relative to the device 20 for using traditional structure to prepare and the device 19 prepared with comparison 1, originally
Invention introduces fluorenes provided by the invention close to luminescent layer side between anode and luminescent layer and carbazole derivates change as efficiency
The organic electroluminescence device that kind layer is prepared has been obviously improved device in the side such as light emission luminance, current efficiency, coloration, service life
Face have excellent performance, be one kind can be widely applied into device architecture with further promoted device electroluminescence characters,
The material layer of thermal stability and service life.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of fluorenes and carbazole derivates, which is characterized in that shown in its general structure such as following formula (I):
Wherein, n is 0 or 1；
Any one X1For C, other X1Independent is CH, CR0Or N；
Any one X2For C, other X2Independent is CH, CR0Or N；
Y is N or P=O；
R1、R2It is independently C6~45Aryl or C3~45Heteroaryl, R1With R2It is identical or different；
The R0Selected from cyano, nitro, C1~20Alkyl, C1~20Alkoxy, C1~20Alkylthio group, C6~45Aryloxy group, C6~45
Arylthio.
2. fluorenes according to claim 1 and carbazole derivates, which is characterized in that
The R1Or R2C6~45Aryl be selected from: by C1~20The substituted or unsubstituted phenyl of alkyl, by C1~20Alkyl replace
Or unsubstituted xenyl, by C1~20The substituted or unsubstituted phenyl napthyl of alkyl, by C1~20Alkyl it is substituted or unsubstituted
Naphthalene, by C1~20The substituted or unsubstituted naphthylphenyl of alkyl, by C1~20The substituted or unsubstituted anthryl of alkyl, by
C1~20The substituted or unsubstituted fluorenyl of alkyl；
The R1Or R2C3~45Heteroaryl be selected from: by C1~20The substituted or unsubstituted benzofuranyl of alkyl, by C1~20's
The substituted or unsubstituted benzothienyl of alkyl, by C1~20The substituted or unsubstituted dibenzofuran group of alkyl, by C1~20's
The substituted or unsubstituted dibenzothiophene of alkyl, by C1~20The substituted or unsubstituted carbazyl of alkyl, by C1~20Alkyl
Substituted or unsubstituted phenyl carbazole base, by C1~20The substituted or unsubstituted carbazyl phenyl of alkyl.
3. fluorenes according to claim 1 and carbazole derivates, which is characterized in that X1Number for N is 0-3, X2For of N
Number is 0~3, n 1.
4. fluorenes according to claim 1 and carbazole derivates, which is characterized in that including chemical combination shown in chemical formula 1-152
Object:
5. the preparation method of a kind of fluorenes as described in claim 1-4 and carbazole derivates, which is characterized in that including walking as follows
It is rapid:
S1. by formula (a) compound represented and formula (b) compound represented investment reactor, the first palladium chtalyst is then put into
Agent, the first Phosphine ligands, the first base reagent and the first solvent, ultrasound remove air, react under nitrogen protection, obtain formula (c) institute
Show compound；
S2. formula (c) compound represented is put into reactor, then puts into the second palladium catalyst, the second Phosphine ligands, the second alkali
Reagent and the second solvent, ultrasound remove air, react under nitrogen protection, obtain compound shown in formula (d)；
S3. by formula (d) compound represented and formula (e) compound represented investment reactor, the catalysis of third copper is then put into
Agent, cocatalyst, third base reagent and third solvent, ultrasound remove air, react under nitrogen protection, obtain formula (f) institute
Show compound；
S4. in the investment reactor of compound shown in formula (f) and formula (g), will then put into the 4th palladium catalyst, the 4th Phosphine ligands,
4th base reagent and the 4th solvent, ultrasound remove air, and reaction obtains the fluorenes and carbazole derivates under nitrogen protection；
Wherein, Z1、Z2、Z3、Z4It is independently selected from Cl, Br, I.
6. the preparation method of fluorenes according to claim 5 and carbazole derivates, which is characterized in that
Formula (a) compound represented described in step S1, formula (b) compound represented, the first palladium catalyst, the first Phosphine ligands,
The feed ratio of first base reagent and the first solvent be 1mmol:0.5~1.5mmol:0.005~0.02mmol:0.005~
0.02mmol:2~4mmol:3~15mL, reaction temperature are 60~80 DEG C, and liquid phase monitoring formula (a) compound represented has been reacted
At compound shown in formula (c) can be obtained in quenching reaction, processing；
Step S2 Chinese style (c) compound represented, the second palladium catalyst, the second Phosphine ligands, the second base reagent and the second solvent
Feed ratio is 1mmol:0.02~0.2mmol:0.01~0.3mmol:2~5mmol:2~10mL, and reaction temperature is 100~165
DEG C, liquid phase monitors the reaction of formula (c) compound represented and completes, and restores room temperature, and compound shown in formula (d) can be obtained in processing；
Step S3 Chinese style (d) compound represented, formula (e) compound represented, third copper catalyst, cocatalyst, third
The feed ratio of base reagent and third solvent be 1mmol:1.1~3mmol:0.1~0.5mmol:0.1~0.5mmol:2~
5mmol:2~10mL, reaction temperature are 100~165 DEG C, and liquid phase monitors the reaction of formula (d) compound represented and completes, recovery room
Temperature, processing, can be obtained compound shown in formula (f)；
Compound shown in formula (f) described in step S4, compound shown in formula (g), the 4th palladium catalyst, the 4th Phosphine ligands, the 4th
The feed ratio of base reagent and the 4th solvent be 1:1~3:0.005~0.02mmol:0.01~0.04mmol:2~4mmol:2~
10mL, reaction temperature are 90~115 DEG C, and liquid phase monitors the reaction of formula (f) compound represented and completes, and restore room temperature, processing
Obtain the fluorenes and carbazole derivates of target.
7. according to the preparation method of the described in any item fluorenes of claim 5-6 and carbazole derivates, which is characterized in that described first
Palladium catalyst is tris(dibenzylideneacetone) dipalladium, and first Phosphine ligands are triphenylphosphine, and first base reagent is tertiary fourth
Sodium alkoxide, first solvent are the mixed solution that second alcohol and water is mixed to get according to the volume ratio of 2:1；Second palladium catalyst
For palladium acetate, second Phosphine ligands are tri-tert-butylphosphine tetrafluoroborate, and second base reagent is potassium carbonate, described second
Solvent is N-Methyl pyrrolidone, and the third copper catalyst is cuprous iodide, and crown ether -6 the cocatalyst 18- are described
Third base reagent is potassium carbonate, and the third solvent is dimethyl acetamide, and the 4th palladium catalyst is three (dibenzylidenes third
Ketone) two palladiums, the 4th Phosphine ligands are tri-tert-butylphosphine tetrafluoroborate, and the 4th base reagent is sodium tert-butoxide, described the
Four solvents are toluene.
8. a kind of application of fluorenes according to any one of claims 1-4 and carbazole derivates in preparation display device.
9. a kind of organic electroluminescence device, the organic electroluminescence device is by a pair of electrodes and interelectrode organic layer structure
At, which is characterized in that the organic layer includes at least hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electronics
Implanted layer, the hole transmission layer and/or luminescent layer include the described in any item fluorenes of claim 1-4 and carbazole derivates.
10. organic electroluminescence device according to claim 9, which is characterized in that the organic layer is injected comprising hole
Layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, and close to the side of luminescent layer in organic layer
Improved efficiency layer, the improved efficiency layer includes the fluorenes and carbazole derivates.
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| CN110128323A (en) * | 2019-03-08 | 2019-08-16 | 武汉尚赛光电科技有限公司 | A kind of fluorenes simultaneously carbazole derivates, preparation method and application |
| CN110526874A (en) * | 2019-08-28 | 2019-12-03 | 武汉华星光电半导体显示技术有限公司 | Fluorenes and phenazene derivative and preparation method thereof and OLED device |
| CN113620858A (en) * | 2020-12-14 | 2021-11-09 | 阜阳欣奕华材料科技有限公司 | Organic electroluminescent compound and preparation method and application thereof |
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| CN105175313A (en) * | 2015-09-02 | 2015-12-23 | 上海道亦化工科技有限公司 | Hole injection compound and organic electroluminescent device |
| WO2018012762A1 (en) * | 2016-07-11 | 2018-01-18 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising same |
| CN109970623A (en) * | 2017-12-28 | 2019-07-05 | 武汉尚赛光电科技有限公司 | Derivative of tri-arylamine group and preparation method thereof, application and device |
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| CN105175313A (en) * | 2015-09-02 | 2015-12-23 | 上海道亦化工科技有限公司 | Hole injection compound and organic electroluminescent device |
| WO2018012762A1 (en) * | 2016-07-11 | 2018-01-18 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising same |
| CN109970623A (en) * | 2017-12-28 | 2019-07-05 | 武汉尚赛光电科技有限公司 | Derivative of tri-arylamine group and preparation method thereof, application and device |
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| CN110128323A (en) * | 2019-03-08 | 2019-08-16 | 武汉尚赛光电科技有限公司 | A kind of fluorenes simultaneously carbazole derivates, preparation method and application |
| CN110526874A (en) * | 2019-08-28 | 2019-12-03 | 武汉华星光电半导体显示技术有限公司 | Fluorenes and phenazene derivative and preparation method thereof and OLED device |
| CN113620858A (en) * | 2020-12-14 | 2021-11-09 | 阜阳欣奕华材料科技有限公司 | Organic electroluminescent compound and preparation method and application thereof |
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