CN107445954A - A kind of electroluminescent organic material, its preparation method and application with fluorenes and ferrosin structure - Google Patents
A kind of electroluminescent organic material, its preparation method and application with fluorenes and ferrosin structure Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention belongs to field of organic electroluminescence, more particularly to a kind of electroluminescent organic material, its preparation method and application with fluorenes and ferrosin structure.New Organic Electro Luminescent Materials provided by the invention are intermolecular to be not easy to crystallize, is not easy to assemble, suitable HOMO and lumo energy, with good heat endurance, glass transition temperature and decomposition temperature are all very high, easily form good amorphous membrance, apply in organic electroluminescence device, more stable effect and longer service life can be obtained.Compound of the present invention can be applied to the making of OLED luminescent devices, and can obtain good device performance, the compound as OLED luminescent devices electron transport material in use, the device of making has good photoelectric properties.
Description
Technical field
The invention belongs to field of organic electroluminescence, more particularly to a kind of organic electroluminescence hair with fluorenes and ferrosin structure
Luminescent material, its preparation method and application.
Background technology
Organic electroluminescent diode (OLED) results from the eighties in last century, has self-luminous, wide viewing angle, response speed
It hurry up, many advantages, such as Flexible Displays can be achieved, this becomes the most favourable competitor of flat panel display of future generation, by people
Greatly concern, and by the development of more than two decades, the technology progressively moves to maturity.
At present, organic electroluminescent technology, mainly it is used in two fields, respectively full-color display and white light shine
It is bright, based on the commodity of OLED Display Techniques, industrialization has been done step-by-step, such as, in commodity such as wisdom mobile phone, curved surface TVs
In, this technology is applied widely.
Material for organic electroluminescence device mainly includes electrode material, electron transport material, luminescent material, wherein
Electron transport material occupies critical positions in OLED.
In order to lift the performance of organic electroluminescence device, the research to electron transport material is particularly significant.Select electronics
Transmission material must is fulfilled for following requirement：1st, there are reversible electrochemical reduction and enough reduction potentials, because electric
The process that son conducts in organic film is a series of redox reaction；2nd, good electron mobility；3rd, it is good into
Film and heat endurance；4th, good photostability.
The content of the invention
There is good electronic transmission performance and higher film forming the technical problem to be solved by the invention is to provide a kind of
Property and heat endurance electroluminescent organic material, its preparation method and the application with fluorenes and ferrosin structure.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organic electroluminescence with fluorenes and ferrosin structure
Luminescent material, its structural formula are as follows：
Wherein, R be carbon number be 1-10 alkyl, carbon number be 6-20 aromatic substituent group or heteroaromatic
Any one in group；
Ar be the carbon number containing at least one of nitrogen, oxygen, sulphur atom be 5-60 aromatic heterocycle, carbon number
For any one in 5-60 aromatic substituent group.
Further, R is methyl or phenyl.
Preferably, Ar is any one in following group：
Second object of the present invention is to provide the above-mentioned electroluminescent organic material with fluorenes and ferrosin structure
Preparation method, step are as follows：
(1) ferrosin -9- boric acid and the chloro- methyl benzoates of the bromo- 5- of 2- are added in solvent, in the protection of inert gas
Lower addition catalyst and alkaline matter, are warming up to backflow, 8-12h are reacted under the conditions of 50-200 DEG C, obtain containing intermediate I
Reaction system；
Wherein, described solvent be toluene, dimethylbenzene, trimethylbenzene, absolute ethyl alcohol, dichloroethanes, chloroform, tetrahydrofuran,
One or both of acetone or ethyl acetate are mixed above；Described catalyst is Pd (OAc)2、Pd(PPh3)4、Pd
(PPh3)2Cl2Or Pd2(dba)3One or both of it is mixed above；Described alkaline matter be sodium tert-butoxide, potassium tert-butoxide,
One or both of anhydrous phosphoric acid potassium, potassium carbonate or cesium carbonate are mixed above；
The structural formula of the intermediate I is：
(2) intermediate I for obtaining step (1) is added in solvent, and -50~-90 are cooled under the protection of inert gas
DEG C, the tetrahydrofuran solution of raw material I is added dropwise, insulation reaction 1-4h is added dropwise, reaction is quenched in ammonium chloride solution, in being contained
The reaction system of mesosome II；
Wherein, described solvent is that one or both of tetrahydrofuran, ether or methyl tertiary butyl ether(MTBE) are mixed above；Institute
It is R-MgBr to state raw material I, R be carbon number be 1-10 alkyl, carbon number be 6-20 aromatic substituent group or aromatic series
Any one in heterocyclic group；
The structural formula of the intermediate II is：
(3) glacial acetic acid and concentrated hydrochloric acid are added in the intermediate II obtained to step (2), is heated up under the protection of inert gas
Backflow, the back flow reaction 6-8h under the conditions of 80-130 DEG C, obtains the reaction system containing intermediate III；
The structural formula of the intermediate III is:
(4) intermediate III, raw material II and alkaline matter that step (3) obtains are added in solvent, in inert gas
Under protection, catalyst and phosphine system part are added into system, 10-12h is reacted under the conditions of 50-200 DEG C, is obtained containing intermediate IV
Reaction system；
Wherein, described alkaline matter is sodium tert-butoxide, potassium tert-butoxide, anhydrous phosphoric acid potassium, potassium acetate, potassium carbonate or carbonic acid
One or both of caesium is mixed above；Described phosphine system part is tri-butyl phosphine；Described solvent be toluene, dimethylbenzene,
Trimethylbenzene, N,N-dimethylformamide or dimethyl acetamide；The catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2Or Pd2(dba)3One or both of it is mixed above；
The structural formula of described raw material II is：
The structural formula of the intermediate IV is:
(5) intermediate IV and raw material III obtained step (4) is added in solvent, under the protection of inert gas, is added
Alkaline matter and catalyst, backflow is warming up to, 4-30h is reacted under the conditions of 0-160 DEG C, is obtained containing the anti-of organic photoelectrical material
Answer system；
Wherein, described solvent is toluene, dimethylbenzene, mesitylene, tetrahydrofuran, dichloroethanes or N, N- dimethyl
One or both of formamide is mixed above；Described catalyst is Pd (dppf)2Cl2、 Pd(PPh3)4With Pd (PPh3)2Cl2One or both of it is mixed above；The alkaline matter be sodium hydride, potassium tert-butoxide, sodium tert-butoxide, butyl lithium just oneself
One or both of alkane solution, potassium acetate, potassium phosphate, potassium carbonate or cesium carbonate are mixed above；
Described raw material III is Ar-X, and Ar is the virtue that the carbon number containing at least one of nitrogen, oxygen, sulphur atom is 5-60
Fragrant race's heterocyclic radical, carbon number be 5-60 aromatic substituent group in any one, X Br, Cl or I；
The structural formula of described organic photoelectrical material is：
Further, described inert gas is that one or both of nitrogen, argon gas or helium are mixed above.
Further, in step (1), the mol ratio of ferrosin -9- boric acid and the chloro- methyl benzoates of the bromo- 5- of 2- is 1：(1.0-
3.0)；The mol ratio of ferrosin -9- boric acid and catalyst is 1：(0.001-0.1)；Ferrosin -9- boric acid and alkaline matter rub
You are than being 1：(1.0-5.0)；
In step (2), raw material I and the mol ratio of intermediate I are (2.0-6.0):1；
In step (3), the dosage of intermediate II and glacial acetic acid is that mass ratio is 1：(5.0-50)；The concentration of the concentrated hydrochloric acid
For 35wt%；
In step (4), the mol ratio of raw material II and intermediate III is (1.0-3.0):1；Alkaline matter and intermediate III
Mol ratio is (1.0-5.0):1；The mol ratio of catalyst and intermediate III is (0.001-0.1):1；Phosphine system part and intermediate
III mol ratio is (0.002-0.2):1；
In step (5), the mol ratio of raw material III and intermediate IV is (1.0-3.0):1；Alkaline matter and intermediate IV
Mol ratio is (1.0-3.0):1；The mol ratio of catalyst and intermediate IV is (0.001-0.1):1.
Compound C01-C30 listed by following formula, it is the representative structure for meeting spirit and principle of the invention, it will be appreciated that list
Following compound structure, it is intended merely to preferably explain the present invention, is not limitation of the present invention.
Third object of the present invention is to provide a kind of above-mentioned organic electroluminescence material with fluorenes and ferrosin structure
Expect the electron transport material as electron transfer layer, make the application in organic electroluminescence device field.
Using when, prepared organic electroluminescence device generally comprise superposition successively ITO Conducting Glass (sun
Pole), hole transmission layer (NPB), luminescent layer (EML), electron transfer layer (TPBI and material of the present invention), electron injecting layer
And cathode layer (Al) (LiF).All functional layers are made of vacuum evaporation process.Used organic compound in such device
The molecular structural formula of thing is as follows.
The beneficial effects of the invention are as follows：
1st, new Organic Electro Luminescent Materials provided by the invention are intermolecular is not easy to crystallize, is not easy to assemble, suitable HOMO
And lumo energy, there is good heat endurance, glass transition temperature and decomposition temperature are all very high, easily form good nothing
Shape film, applies in organic electroluminescence device, can obtain more stable effect and longer service life.
2nd, compound of the present invention can be applied to the making of OLED luminescent devices, and can obtain good device table
It is existing, the compound as OLED luminescent devices electron transport material in use, the device of making has good photo electric
Energy.
Brief description of the drawings
Fig. 1 is the structural representation of organic electroluminescence device of the present invention；
In figure, 1, ITO Conducting Glass；2nd, hole transmission layer；3rd, luminescent layer；4th, electron transfer layer；5th, electron injection
Layer；6th, cathode layer.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1 prepares intermediate 1- IV, and reaction equation is as follows：
(1) intermediate 1- I preparation：In 1L there-necked flasks, ferrosin -9- boric acid (44.8g, 0.20mol), 2- are added
The bromo- chloro- methyl benzoates of 5- (52.4g, 0.21mol), potassium carbonate (55.2g, 0.40mol), 165.6g water, Pd (PPh3)4
(2.312g, 2.0mmol), toluene (300mL) and absolute ethyl alcohol (100mL), nitrogen protection, it is warming up to backflow, 70-75 DEG C of insulation
10h is reacted, stops reacting, 25 DEG C is cooled to, liquid separation, collects organic phase, is washed to neutrality, organic phase decompression is sloughed solvent, used
Pure toluene column chromatography purifies, and toluene, petroleum ether recrystallization, obtains intermediate 1- I, yield 78.37%；
(2) intermediate 1- II preparation：Above-mentioned intermediate 1- I (34.9g, 0.10mol) is added in 1L there-necked flasks, added
Enter 400g tetrahydrofurans, be cooled to -78 DEG C, the tetrahydrofuran solution (0.30mol) of methyl-magnesium-bromide is added dropwise, is added dropwise, -78
DEG C insulation reaction 2h, add 200mL saturated ammonium chloride solutions that reaction, liquid separation, washing, organic phase decompression desolventizing, column chromatography is quenched
Purifying, obtains intermediate 1- II, yield 87.67%；
(3) intermediate 1- III preparation：In 500mL there-necked flasks, intermediate 1- II (27.9g, 0.08mol), ice are added
Acetic acid (300g) and 35wt% concentrated hydrochloric acids (1.0g), under nitrogen protection, backflow is warming up to, has gray solid gradually to separate out, flowed back
Lower insulation reaction 8h, 25 DEG C are cooled to, filtered, absolute ethyl alcohol elution filter cake, using toluene as solvent recrystallization, obtain intermediate 1-
III, yield 73.31%；
(4) intermediate 1- IV preparation：In 500mL there-necked flasks, lead under nitrogen protection, add intermediate 1- III
(16.5g, 0.05mol), 15.2g (0.06mol) raw material II, 7.8g (0.08mol) potassium acetate, 0.60g Pd2(dba)3、
0.40g tri-butyl phosphines and 200ml toluene, the insulation reaction 12h under the conditions of 105-110 DEG C, stop reacting, and are cooled to 25 DEG C, mistake
Filter, filtrate decompression desolventizing, the purifying of toluene column chromatography, toluene, petroleum ether are recrystallized to give intermediate 1- IV, yield 75.46%.
High resolution mass spectrum, molecular formula C27H27BN2O2, theoretical value 422.2166, test value 422.2187.
Using intermediate 1- IV made from embodiment 1 as embodiment 3-7 reaction raw materials.
Embodiment 2 prepares intermediate 2- IV, and reaction equation is as follows：
With reference to embodiment 1, the raw material methyl-magnesium-bromide in step (2) is replaced by phenyl-magnesium-bromide, obtained by preparation process
Intermediate 2- IV, yield 35.61%.
High resolution mass spectrum, molecular formula C37H31BN2O2, theoretical value 546.2479, test value 546.2458.
Using intermediate 2- IV made from embodiment 2 as embodiment 8-11 reaction raw materials.
The compound C01 of embodiment 3 synthesis
In 250mL there-necked flasks, lead under nitrogen protection, add intermediate 1- IV (4.22g, 0.01mol), 2- bromopyridines
(1.74g, 0.011mol), potassium carbonate (4.14g, 0.03mol), 12.5g water, Pd (PPh3)4(0.116g, 0.1mmol), toluene
(50mL) and absolute ethyl alcohol (20mL), is warming up to backflow, in 70-75 DEG C of insulation reaction 10 hours, stops reacting, is cooled to 25 DEG C,
Liquid separation, organic phase is collected, is washed to neutrality, solvent is sloughed in organic phase decompression, is purified using pure toluene column chromatography, toluene, anhydrous
Ethyl alcohol recrystallization, obtain compound C01, yield 82.40%.
High resolution mass spectrum, molecular formula C26H19N3, theoretical value 373.1579, test value 373.1591.
The compound C05 of embodiment 4 synthesis
With reference to embodiment 3, raw material 2- bromopyridines are replaced with 9- bromines phenanthrene by preparation process, obtain compound C05, yield
79.47%.
High resolution mass spectrum, molecular formula C35H24N2, theoretical value 472.1939, test value 472.1928.
The compound C07 of embodiment 5 synthesis
With reference to embodiment 3, raw material 2- bromopyridines are replaced with bromo- 2, the 6- hexichol yl pyridines of 4-, obtain chemical combination by preparation process
Thing C07, yield 76.72%.
High resolution mass spectrum, molecular formula C38H27N3, theoretical value 525.2205, test value 525.2214.
The compound C10 of embodiment 6 synthesis
With reference to embodiment 3, raw material 2- bromopyridines are replaced with bromo- 4, the 6- diphenyl -1,3,5-triazines of 2- by preparation process,
Obtain compound C10, yield 77.04%.
High resolution mass spectrum, molecular formula C36H25N5, theoretical value 527.2110, test value 527.2124.
The compound C13 of embodiment 7 synthesis
With reference to embodiment 3, raw material 2- bromopyridines are replaced with 2- (4- bromophenyls) -1- phenyl -1H- benzo miaows by preparation process
Azoles, obtain compound C13, yield 78.16%.
High resolution mass spectrum, molecular formula C40H28N4, theoretical value 564.2314, test value 564.2310.
The compound C19 of embodiment 8 synthesis
With reference to embodiment 3, raw material midbody 1- IV and 2- bromopyridines are replaced with the Hes of intermediate 2- IV by preparation process respectively
4- bromine triphenylamines, obtain compound C19, yield 75.38%.
High resolution mass spectrum, molecular formula C49H33N3, theoretical value 663.2674, test value 663.2668.
The compound C23 of embodiment 9 synthesis
With reference to embodiment 3, raw material midbody 1- IV and 2- bromopyridines are replaced with the Hes of intermediate 2- IV by preparation process respectively
3,5- bipyridyl bromobenzenes, obtain compound C23, yield 72.49%.
High resolution mass spectrum, molecular formula C47H30N4, theoretical value 650.2470, test value 650.2461.
The compound C29 of embodiment 10 synthesis
With reference to embodiment 3, raw material midbody 1- IV and 2- bromopyridines are replaced with the Hes of intermediate 2- IV by preparation process respectively
9- (3- bromophenyls) -9H- carbazoles, obtain compound C29, yield 74.17%.
High resolution mass spectrum, molecular formula C49H31N3, theoretical value 661.2518, test value 661.2527.
The compound C30 of embodiment 11 synthesis
Carried out with reference to embodiment 3, raw material midbody 1- IV and 2- bromopyridines are replaced with into intermediate 2- IV and 2- bromines respectively
Triphenylene, obtain compound C30, yield 68.75%.
High resolution mass spectrum, molecular formula C49H30N2, theoretical value 646.2409, test value 646.2418.
The present invention chooses compound C01, compound C05, compound C07, compound C10, compound C13, compound
C19, compound C23, compound C29, compound C30 make organic electroluminescence device as electron transfer layer.
It should be appreciated that device implementation process and result, are intended merely to preferably explain the present invention, not to the limit of the present invention
System.
Application examples 1
Applications of the compound C01 in organic electroluminescence device：
A) ITO (tin indium oxide) glass is cleaned：Respectively each 30 points of ito glass is cleaned with deionized water, acetone, EtOH Sonicate
Clock, then handled 5 minutes in plasma cleaner；
B) the vacuum evaporation hole transmission layer NPB on anode ito glass, thickness 50nm；
C) on hole transmission layer NPB, vacuum evaporation luminescent layer compound EML, thickness 30nm；
D) on luminescent layer, vacuum mixing evaporation is used as electron transfer layer C01, thickness 30nm；
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness 1nm；
F) on electron injecting layer, vacuum evaporation negative electrode Al, thickness 100nm.
The structure of device one is ITO/NPB (50nm)/EML (30nm)/C01 (30nm)/LiF (1nm)/Al (100nm),
Material of main part using compound C01 as device one, obtained device test result are shown in Table 1.
Application examples 2-9 luminescent layer by the compound C01 in application examples 1 replace with respectively compound C05, compound C07,
Compound C10, compound C13, compound C19, compound C23, compound C29 and compound C30, device two is made to device
Part nine.
Comparative example
Compound C01 in application examples 1 is replaced with into compound TPBI, device ten is made.The structure of device ten is ITO/
NPB(50nm)/EML(30nm)/TPBI(30nm)/LiF(1nm)/Al(100nm)；Obtained device test result is shown in Table 1.
Table 1
By above-mentioned table 1 it is known that photoelectric material of the present invention can be applied to the making of organic electroluminescence device, and
And good performance can be obtained.Material of the present invention uses as the electron transport material of organic electroluminescence device, device
The driving voltage of part one to nine is significantly lower than the comparative device ten for using conventional TPBI as electron transport material.In addition, with
Comparative device ten is compared, and high-high brightness, current efficiency and excitation of device one to nine etc. have clear improvement.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (7)
1. a kind of electroluminescent organic material with fluorenes and ferrosin structure, it is characterised in that its structural formula is as follows：
Wherein, R be carbon number be 1-10 alkyl, carbon number be 6-20 aromatic substituent group or aromatic heterocyclic group
In any one；
Ar be the carbon number containing at least one of nitrogen, oxygen, sulphur atom be 5-60 aromatic heterocycle, carbon number 5-
60 aromatic substituent group in any one.
2. electroluminescent organic material according to claim 1, it is characterised in that R is methyl or phenyl.
3. electroluminescent organic material according to claim 1, it is characterised in that Ar is any one in following group
Kind：
4. there is the preparation method of fluorenes and the electroluminescent organic material of ferrosin structure, its feature described in a kind of claim 1
It is, step is as follows：
(1) ferrosin -9- boric acid and the chloro- methyl benzoates of the bromo- 5- of 2- are added in solvent, added under the protection of inert gas
Enter catalyst and alkaline matter, be warming up to backflow, 8-12h is reacted under the conditions of 50-200 DEG C, obtain the reaction containing intermediate I
System；
Wherein, described solvent is toluene, dimethylbenzene, trimethylbenzene, absolute ethyl alcohol, dichloroethanes, chloroform, tetrahydrofuran, acetone
Or one or both of ethyl acetate is mixed above；Described catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2
Or Pd2(dba)3One or both of it is mixed above；Described alkaline matter is sodium tert-butoxide, potassium tert-butoxide, anhydrous phosphoric acid
One or both of potassium, potassium carbonate or cesium carbonate are mixed above；
The structural formula of the intermediate I is：
(2) intermediate I for obtaining step (1) is added in solvent, -50~-90 DEG C is cooled under the protection of inert gas, drop
Add the tetrahydrofuran solution of raw material I, insulation reaction 1-4h is added dropwise, reaction is quenched in ammonium chloride solution, and acquisition contains intermediate
II reaction system；
Wherein, described solvent is that one or both of tetrahydrofuran, ether or methyl tertiary butyl ether(MTBE) are mixed above；The original
Material I be R-MgBr, R be carbon number be 1-10 alkyl, carbon number be 6-20 aromatic substituent roll into a ball or heteroaromatic
Any one in group；
The structural formula of the intermediate II is：
(3) glacial acetic acid and concentrated hydrochloric acid are added in the intermediate II obtained to step (2), is heated up back under the protection of inert gas
Stream, the back flow reaction 6-8h under the conditions of 80-130 DEG C, obtains the reaction system containing intermediate III；
The structural formula of the intermediate III is:
(4) intermediate III, raw material II and alkaline matter that step (3) obtains are added in solvent, in the protection of inert gas
Under, catalyst and phosphine system part are added into system, 10-12h is reacted under the conditions of 50-200 DEG C, is obtained containing the anti-of intermediate IV
Answer system；
Wherein, described alkaline matter is in sodium tert-butoxide, potassium tert-butoxide, anhydrous phosphoric acid potassium, potassium acetate, potassium carbonate or cesium carbonate
One or more kinds of mixing；Described phosphine system part is tri-butyl phosphine；Described solvent is toluene, dimethylbenzene, front three
Benzene, N,N-dimethylformamide or dimethyl acetamide；The catalyst is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2Or
Pd2(dba)3One or both of it is mixed above；
The structural formula of described raw material II is：
The structural formula of the intermediate IV is:
(5) intermediate IV and raw material III obtained step (4) is added in solvent, under the protection of inert gas, adds alkalescence
Material and catalyst, backflow is warming up to, 4-30h is reacted under the conditions of 0-160 DEG C, obtain the reactant containing organic photoelectrical material
System；
Wherein, described solvent is toluene, dimethylbenzene, mesitylene, tetrahydrofuran, dichloroethanes or DMF
One or both of it is mixed above；Described catalyst is Pd (dppf)2Cl2、Pd(PPh3)4With Pd (PPh3)2Cl2In one
Kind or two or more mixing；The alkaline matter is sodium hydride, potassium tert-butoxide, sodium tert-butoxide, the hexane solution of butyl lithium, vinegar
One or both of sour potassium, potassium phosphate, potassium carbonate or cesium carbonate are mixed above；
Described raw material III is Ar-X, and Ar is the aromatic series that the carbon number containing at least one of nitrogen, oxygen, sulphur atom is 5-60
Heterocyclic radical, carbon number be 5-60 aromatic substituent group in any one, X Br, Cl or I；
The structural formula of described organic photoelectrical material is：
5. preparation method according to claim 4, it is characterised in that described inert gas is nitrogen, argon gas or helium
One or both of it is mixed above.
6. preparation method according to claim 4, it is characterised in that in step (1), ferrosin -9- boric acid and the bromo- 5- of 2-
The mol ratio of chloro- methyl benzoate is 1：(1.0-3.0)；The mol ratio of ferrosin -9- boric acid and catalyst is 1：(0.001-
0.1)；The mol ratio of ferrosin -9- boric acid and alkaline matter is 1：(1.0-5.0)；
In step (2), raw material I and the mol ratio of intermediate I are (2.0-6.0):1；
In step (3), the dosage of intermediate II and glacial acetic acid is that mass ratio is 1：(5.0-50)；The concentration of the concentrated hydrochloric acid is
35wt%；
In step (4), the mol ratio of raw material II and intermediate III is (1.0-3.0):1；Mole of alkaline matter and intermediate III
Than for (1.0-5.0):1；The mol ratio of catalyst and intermediate III is (0.001-0.1):1；Phosphine system part and intermediate III
Mol ratio is (0.002-0.2):1；
In step (5), the mol ratio of raw material III and intermediate IV is (1.0-3.0):1；Mole of alkaline matter and intermediate IV
Than for (1.0-3.0):1；The mol ratio of catalyst and intermediate IV is (0.001-0.1):1.
7. there is the electricity of fluorenes and the electroluminescent organic material of ferrosin structure as electron transfer layer described in a kind of claim 1
Sub- transmission material, making the application in organic electroluminescence device field.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006449A1 (en) * | 2006-07-11 | 2008-01-17 | Merck Patent Gmbh | Novel materials for organic electroluminescent devices |
| CN102127073B (en) * | 2010-11-26 | 2014-07-23 | 深圳大学 | Star-shaped compound taking phenanthroline as core and luminescent device comprising same |
| US20160141502A1 (en) * | 2014-11-19 | 2016-05-19 | Lg Display Co., Ltd. | Organic light emitting display device |
| CN105655496A (en) * | 2014-11-14 | 2016-06-08 | Sfc株式会社 | Organic luminescence compound and organic electroluminescence element containing organic luminescence compound |
| CN106749236A (en) * | 2016-12-06 | 2017-05-31 | 中节能万润股份有限公司 | A kind of new aza toroid electroluminescent organic material and its application with dibenzocycloheptene structure |
-
2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006449A1 (en) * | 2006-07-11 | 2008-01-17 | Merck Patent Gmbh | Novel materials for organic electroluminescent devices |
| CN102127073B (en) * | 2010-11-26 | 2014-07-23 | 深圳大学 | Star-shaped compound taking phenanthroline as core and luminescent device comprising same |
| CN105655496A (en) * | 2014-11-14 | 2016-06-08 | Sfc株式会社 | Organic luminescence compound and organic electroluminescence element containing organic luminescence compound |
| US20160141502A1 (en) * | 2014-11-19 | 2016-05-19 | Lg Display Co., Ltd. | Organic light emitting display device |
| CN105609522A (en) * | 2014-11-19 | 2016-05-25 | 乐金显示有限公司 | Organic light emitting display device |
| CN106749236A (en) * | 2016-12-06 | 2017-05-31 | 中节能万润股份有限公司 | A kind of new aza toroid electroluminescent organic material and its application with dibenzocycloheptene structure |
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