CN110467577A - Phenanthro- pyrimidine derivatives and its application in an organic light emitting device - Google Patents

Phenanthro- pyrimidine derivatives and its application in an organic light emitting device Download PDF

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CN110467577A
CN110467577A CN201810440684.5A CN201810440684A CN110467577A CN 110467577 A CN110467577 A CN 110467577A CN 201810440684 A CN201810440684 A CN 201810440684A CN 110467577 A CN110467577 A CN 110467577A
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synthesis
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孙恩涛
刘叔尧
邵爽
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Abstract

A kind of organic compound is indicated by leading to formula (I) as follows:Wherein, Ar1Substituted or unsubstituted aryl selected from C6~C60；Ar2The heteroaryl of substituted or unsubstituted aryl selected from C6~C60, C6~C30 containing pyridine groups；L1、L2The separately arlydene selected from singly-bound, C6~C14；R1~R9Separately it is selected from the substituted or unsubstituted heteroaryl of hydrogen, halogen, cyano, the alkyl of C1~C12, the substituted or unsubstituted aryl of C6~C30, C3~C30；When the aryl or heteroaryl have substituent group, which is selected from the aryl of the alkyl of C1~C8, C6~C30.

Description

Phenanthro- pyrimidine derivatives and its application in an organic light emitting device
Technical field
The present invention relates to a kind of new organic heterocyclic molecules, more particularly to one kind to contain the organic of phenanthro- pyrimidine group Object and its derivative and their applications in organic electroluminescence device.
Background technique
Now with OLED technology in the continuous propulsion for showing and illuminating two big fields, people are for its core material Research focuses more on, and industry has been devoted to develop luminous effect of the new electroluminescent organic material to further increase device Rate and service life.
In general, common electron transport material such as A1Q3The electron mobility of (8-hydroxyquinoline aluminum) is remote low In the hole mobility of hole mobile material, thus the injection and transmission that on the one hand will lead to carrier in OLED device are not It is balanced and caused by the recombination probability of hole and electronics reduce, to reduce the luminous efficiency of device, on the other hand have lower The operating voltage that the electron transport material of electron mobility will lead to device increases, to influence power efficiency.
In order to solve this problem, patent document 1 discloses a kind of compound, wherein the nitrogenous heteroaryl of such as triazine It is bonded on the nitrogen-atoms of benzo carbazole as organic electroluminescent compounds；Patent document 2 discloses a kind of compound, contains Naphtho- pyrimidine group is bonded on heterocyclic aryl as organic electroluminescent compounds.With A1Q3As electron transport material phase Than the voltage of the organic electroluminescence device for the compound for having used patent document 1 and 2 to obtain decreases, and efficiency is mentioned It rises.
Existing technical literature
Patent document
Patent document 1:KR10-1074193
Patent document 2:WO2015/182769
Summary of the invention
Problems to be solved by the invention
However, mobility is still lower, causes when status is that compound in the prior art is used as electron transport material It is still higher using the driving voltage of the organic electroluminescence device of the material and luminous efficiency is still not high enough, it is not able to satisfy The demand and mobile electronic device that OLED device constantly promotes photoelectric properties are for energy-efficient demand.Therefore, exploitation is new With high mobility electron transport material tool have very important significance.
Solution to problem
The present invention provides a kind of new compound for being used for organic electroluminescence device.The compound is by introducing phenanthro- Pyrimidine group realizes good electronic transmission performance.
Specifically, the present invention provides a kind of organic compound, indicated by leading to formula (I) as follows:
Wherein, Ar1Aryl selected from substituted or unsubstituted C6~C60 (not including the carbon number of substituent group, similarly hereinafter) (if not specified, the aryl in the application includes fused ring aryl)；
Ar2Aryl selected from substituted or unsubstituted C6~C60, C6~C30 containing pyridine groups heteroaryl (if not It illustrates, the heteroaryl in the application includes fused ring heteroaryl)；
L1、L2The separately arlydene selected from singly-bound, C6~C14, is preferably selected from singly-bound, phenylene, naphthylene, more Preferably singly-bound；
R1~R9Separately it is selected from hydrogen, halogen, cyano, the alkyl of C1~C12, substituted or unsubstituted C6~C30 Aryl, substituted or unsubstituted C3~C30 heteroaryl (preferably fused ring heteroaryl), preferably separately be selected from hydrogen, halogen The heteroaryl of element, cyano, the alkyl of C1~C8, the aryl of substituted or unsubstituted C6~C24, substituted or unsubstituted C3~C24 Base；
When above-mentioned aryl or heteroaryl have substituent group, which is selected from the virtue of the alkyl of C1~C8, C6~C30 Base is preferably selected from the alkyl of C1~C8, the aryl of C6~C24.
The study found that can be effectively reduced and use when the compounds of this invention is used in OLED as electron transport material The driving voltage of the organic electroluminescence device of the compound, while the service life of material is improved, concrete reason is still not clear, Speculate the possible reason is, the compounds of this invention includes that phenanthro- pyrimidine structure is conducive to the injection of electronics as electron-withdrawing group, Therefore the driving voltage of device is minimized；The precursor structure of the phenanthro- pyrimidine of the compound of the present invention has conjugated polycyclic special Property, the size of conjugated system is suitable, and flatness is good, has good thermal stability, be conducive to intermolecular solid-state accumulation, because The service life of this material is promoted；In addition, as the phenanthro- pyrimidine structure of electron-withdrawing group, as giving in the compounds of this invention The unazotized aryl Ar of electron group1And can be used as electron-withdrawing group (heteroaryl containing pyridine) can also be used as to The Ar of electron group (aryl)2Between across a phenyl ring, and 1,3,5 for being connected to phenyl ring (are between any two Meta position relationship), effectively prevent the association between each group of intramolecular, may be also the service life improve the reason of one of.
In above-mentioned logical formula (I), R1~R8Separately it is preferably selected from hydrogen, halogen, cyano, methyl, ethyl, propyl, benzene Base, naphthalene are further preferably selected from hydrogen, chlorine, cyano, methyl, ethyl, most preferably hydrogen.R9It is preferably selected from methyl, ethyl, ring Hexyl, phenyl, naphthalene, more preferably methyl or phenyl, most preferably phenyl.By by R9Above-mentioned group is set as to replace Reactive hydrogen atom on pyrimidine ring can further increase the stability of the compounds of this invention.
In above-mentioned logical formula (I), Ar1Aryl selected from substituted or unsubstituted C6~C60.Ar1The substitution that is selected from does not take The aryl of the C6~C60 in generation refers to the aromatics ring system with 6 to 60 ring skeleton carbon atoms, including single ring architecture substituent group Such as phenyl etc. also includes being covalently attached the aromatic ring substituents group of structure such as xenyl, terphenyl, further includes condensed ring Structure substituent group such as naphthalene, anthryl, phenanthryl, fluoranthene base etc., condensed cyclic structure substituent group is connected with single ring architecture aryl Building stone such as benzene binaphthyl, naphthalene xenyl, biphenyl dianthranide base etc., and be covalently attached the thick aromatic ring substituents of structure Group is such as binaphthyl.Above-mentioned aryl preferably has 6 to 40 ring skeleton carbon atoms, more preferably has 6 to 30 ring skeleton carbon Atom most preferably has 6 to 20 ring skeleton carbon atoms.The specific example of above-mentioned aryl is as follows:
Further, in logical formula (I) of the invention, Ar1It is preferably selected from phenyl, xenyl, anthryl, naphthalene, phenanthryl, glimmering Anthryl, base, triphenylene (9,10- benzophenanthrene), 9,9- dimethyl fluorenyl, Spirofluorene-based, benzene binaphthyl, naphthalene xenyl, it is more excellent Choosing is selected from phenyl, xenyl, anthryl, phenanthryl, fluoranthene base, base, further preferably phenanthryl.
The study found that by Ar1In the case where being set as above-mentioned unazotized aromatic group, the present invention is as electron-transport When material is in OLED, the service life of organic electroluminescence device can be further increased, concrete reason is still not clear, and pushes away Survey the possible reason is, the steric hindrance of above-mentioned aromatic group is of moderate size, and is conducive to the stability of molecule itself and intermolecular Solid-state accumulation, therefore the service life of material and device is promoted.
Work as Ar1When above having substituent group, which is preferably selected from the simple aryl of substituted or unsubstituted C6~C30 (that is, the not aryl of condensed cyclic structure), more preferably phenyl or naphthyl, further preferably phenyl.
In above-mentioned logical formula (I), Ar2Aryl or C6~C30 selected from substituted or unsubstituted C6~C60 contain pyridine groups Heteroaryl.
Ar2Aryl selected from substituted or unsubstituted C6~C60 refers to the aromatics with 6 to 60 ring skeleton carbon atoms Ring system, including single ring architecture substituent group such as phenyl etc. also include the aromatic ring substituents group such as biphenyl for being covalently attached structure Base, terphenyl, binaphthyl etc. further include condensed cyclic structure substituent group such as naphthalene, anthryl, phenanthryl, fluoranthene base etc., condensed ring The building stone that structure substituent group is connected with single ring architecture aryl such as benzene binaphthyl, naphthalene xenyl, biphenyl dianthranide base Deng, and the thick aromatic ring substituents group of structure is covalently attached such as binaphthyl.Above-mentioned aryl preferably has 6 to 40 ring bones Frame carbon atom more preferably has 6 to 30 ring skeleton carbon atoms, most preferably has 6 to 20 ring skeleton carbon atoms.
Ar2The heteroaryl for the C6~C30 containing pyridine groups being selected from refers to that the heteroaryl structure of C6~C30 passes through covalent bond It is connected with the heteroaryl of the pyridine such as pyridine, phenylpyridine or derivatives thereof group.Above-mentioned heteroaryl preferably has 6 to 14 The heteroaryl structure of a ring skeleton carbon atom.The specific example of above-mentioned heteroaryl is as follows:
Ar2It is preferably selected from phenyl, naphthalene, pyridyl group, bipyridyl, phenylpyridyl, naphthlypyridine base, phenyl napthyl Pyridyl group, naphthylphenyl pyridyl group, xenyl pyridyl group, pyridinylphenyl pyridyl group, pyridyl group naphthlypyridine base, quinolyl Pyridyl group.
Ar2More preferably C6~C30 heteroaryl containing pyridine groups, further preferably selected from pyridyl group (at this point, L2For list Key, phenylene or naphthylene), bipyridyl, phenylpyridyl, naphthlypyridine base, phenyl napthyl pyridyl group, naphthylphenyl pyrrole Piperidinyl, xenyl pyridyl group, pyridinylphenyl pyridyl group, pyridyl group naphthlypyridine base, quinolyl pyridyl group, most preferably pyrrole Piperidinyl or phenylpyridyl.
The study found that by Ar2In the case where being set as above-mentioned group, the present invention is used for OLED as electron transport material When middle, the current efficiency of organic electroluminescence device can be significantly improved, concrete reason is still not clear, thus it is speculated that possible original Because being, pyridine groups have electron attraction, therefore introduce the compounds of this invention tool of the above-mentioned group comprising pyridine groups There is high electron injection ability.
Further, the organic compound that logical formula (I) of the invention indicates can preferably in detail below structure A1-A72 One of, but these compounds are only representative.
The invention further relates to application of the above-mentioned organic compound in organic electroluminescence device, especially in Organic Electricity As the application of electron transport material in electroluminescence device.
The present invention provides a kind of organic electroluminescence device, including first electrode, second electrode and is inserted in described first If the dried organic layer between electrode and second electrode, which is characterized in that contain above-mentioned organic compound in the organic layer.
In above-mentioned organic electroluminescence device, the compound is preferably used as electron transport layer materials, electron injecting layer Material or emitting layer material.
Invention effect
In the compounds of this invention, the precursor structure of the phenanthro- pyrimidine of the conjugated polycyclic characteristic as electron-withdrawing group, conduct The unazotized aryl Ar of electron donating group1And it can be used as electron-withdrawing group and can also be used as the Ar of electron donating group2Even The 1 of the same phenyl ring is connected to, on 3,5.The compounds of this invention has good thermal stability.Using the compounds of this invention as When electron transport material is in OLED, current efficiency can be significantly improved, reduce driving voltage and extends device lifetime, it can To meet the needs of OLED device is to photoelectric properties.
In addition, preparation is simple for the compounds of this invention, raw material is easy to get, and is suitble to volume production amplification.
Specifically, the compound in above-mentioned logical formula (I) can be but not limited to be used as in organic electroluminescence device Emitting layer material.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, the present invention is made With reference to embodiment It is further described.
The compound that the present invention mentions can synthesize to obtain by Suzuki coupling reaction, pass through benzo pyrimidine derivatives The molecule coupling labeled of boric acid ester structure, preferably synthetic compound A1-A50 are had on the upper halogen of C0 and aryl.Wherein C0 passes through business Approach purchase obtains.
The compound for the synthetic method that do not mention in the present invention is all the raw produce being obtained through commercial channels.It is real It applies various chemicals used in example and such as joins pinacol borate, potassium carbonate, potassium acetate, [1,1 '-bis- (diphenylphosphinos) Ferrocene] palladium chloride, four triphenyl phosphorus palladiums and dioxane, tetrahydrofuran, dimethylbenzene, the basic chemical industries raw material such as ethyl alcohol It chemical products can be commercially available at home.The some aryl class halides C1-C50 used in embodiment are to pass through business Approach obtains, and directly buys or customize synthesis gained from existing domestic and international supplier.
The analysis detection of intermediate and compound in the present invention uses AB SCIEX mass spectrograph (4000QTRAP) and cloth Luke Nuclear Magnetic Resonance (400M).
Synthetic example:
The specific preparation method of above-mentioned noval chemical compound of the invention will be described in detail by taking multiple synthetic examples as an example below, But preparation method of the invention is not limited to this multiple synthetic example, and those skilled in the art can be on its basis not Any modification, equivalent substitution, improvement and etc. are carried out under the premise of deviating from principle of the present invention, and this method are expanded to of the invention Within the scope of the claimed technical solution of claims.
The synthesis of 1. compound A1 of synthetic example
Under nitrogen protection, using C1 as starting material, 10g C1 (0.02mol) is dissolved in 200 mL1, 4- dioxy six 7.5g connection pinacol borate (0.024mol), 7.2g KOAc (0.1mol) and 0.89g [1,1 '-bis- (hexichol are added in ring Base phosphino-) ferrocene] palladium chloride (0.0012mol), return stirring is overnight.End of reaction is extracted with EA, collects organic phase Too short silicagel column filters out palladium catalyst, and obtained filtrate is concentrated, and addition ethyl alcohol, which boils, to be washed half an hour, filters, collects solid, very 9g white solid intermediate 1, yield 80% are obtained after sky is dry.
Under nitrogen protection, 9g (0.02mol, 1eq.) intermediate 1,9gK is added into 500mL there-necked flask2CO3, it is dissolved in four Benzo pyrimidine derivatives C08.2g is added in the mixed solution 250ml of the mixed solution of hydrogen furans and water (volume ratio 4: 1) (20mol, 1eq), tetra- triphenyl phosphorus palladium of 0.091g open stirring, are heated to 80 DEG C of reflux, react 5h, have insoluble matter in system It is precipitated.Reaction solution is cooled to room temperature, filtering, by the insoluble matter filtered out washing three times, collect solid, boiled with the dimethylbenzene of 1L it is molten, Short silicagel column is rushed while hot, and filtrate is cooling to be precipitated, and white solid powder A1 compound 6.47g, yield 60% is obtained by filtration.
The magnetic resonance spectroscopy data of compound A 1:
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.55 (s, 2H), 8.24 (d, J =28.0Hz, 5H), 7.62 (dt, J=16.0,8.0Hz, 6H), 7.55-7.41 (m, 5H), 7.21-7.04 (m, 5H)
The synthesis of 2. compound A2 of synthetic example
Under nitrogen protection, using C2 as starting material, 10g C2 (0.02mol) is dissolved in 200 mL1, 4- dioxy six 7.5g connection pinacol borate (0.024mol), 7.8g KOAc (0.1mol) and 0.89g [1,1 '-bis- (hexichol is added in ring Base phosphino-) ferrocene] palladium chloride (0.0012mol), return stirring is overnight.End of reaction is extracted with EA, collects organic phase Too short silicagel column filters out palladium catalyst, and obtained filtrate is concentrated, and addition ethyl alcohol, which boils, to be washed half an hour, filters, collects solid, very 9.3g white solid intermediate 1, yield 81% are obtained after sky is dry.
Under nitrogen protection, 9g (0.02mol, 1eq.) intermediate 2,9gK is added into 500mL there-necked flask2CO3, it is dissolved in four Benzo pyrimidine derivatives C07.6g is added in the mixed solution 250ml of the mixed solution of hydrogen furans and water (volume ratio 4: 1) (0.022mol, 1.1eq), tetra- triphenyl phosphorus palladium of 0.091g open stirring, are heated to 80 DEG C of reflux, react 5h, have in system Insoluble matter is precipitated.Reaction solution is cooled to room temperature, filtering, three times by the insoluble matter filtered out washing, solid is collected, with the diformazan of 1L Benzene boils molten, rushes short silicagel column while hot, filtrate is cooling to be precipitated, and white solid powder A1 compound 6.8g, yield is obtained by filtration 57%.
The magnetic resonance spectroscopy data of compound A2:
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.23 (d, J=13.7Hz, 2H), 7.98 (s, 1H), 7.82-7.29 (m, 10H), 7.17 (t, J=24.0Hz, 4H)
The synthesis of 3. compound A-13 of synthetic example
Under nitrogen protection, using C3 as starting material, 10g C3 (0.02mol) is dissolved in 200 mL1, 4- dioxy six 7.4g connection pinacol borate (0.024mol), 7.1g KOAc (0.1mol) and 0.89g [1,1 '-bis- (hexichol are added in ring Base phosphino-) ferrocene] palladium chloride (0.0012mol), return stirring is overnight.End of reaction is extracted with EA, collects organic phase Too short silicagel column filters out palladium catalyst, and obtained filtrate is concentrated, and addition ethyl alcohol, which boils, to be washed half an hour, filters, collects solid, very 8.8g white solid intermediate 1, yield 70% are obtained after sky is dry.
Under nitrogen protection, 8.5g (0.02mol, 1eq.) intermediate 3,8.6gK is added into 500mL there-necked flask2CO3, molten In mixed solution (volume ratio 4: 1) 250ml of tetrahydrofuran and water, be added benzo pyrimidine derivatives C08.2g (20mol, 1eq), tetra- triphenyl phosphorus palladium of 0.091g opens stirring, is heated to flowing back, and reacts 20h, has insoluble matter precipitation in system.Reaction Liquid is cooled to room temperature, filtering, three times by the insoluble matter filtered out washing, is collected solid, is boiled with the dimethylbenzene of 1L molten, rush while hot short Silicagel column, filtrate is cooling to be precipitated, and white solid powder A1 compound 5.32g, yield 58% is obtained by filtration.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.21 (d, J=2.0Hz, 3H), 7.87 (s, 1H), 7.73 (d, J=16.0Hz, 5H), 7.61 (t, J=12.0Hz, 3H), (7.55-7.32 m, 10H)
The synthesis of 4. compound A4 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C4, passes through the synthesis of two-step reaction, purifying Obtain white solid 7.32g, yield 58.3%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.55 (s, 3H), 8.37-8.17 (m, 8H), 7.73-7.35 (m, 13H), 7.13 (d, J=20.0Hz, 2H)
The synthesis of 5. compound A-45 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C5, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.9g, yield 60.5%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 2H), 8.88 (d, J=32.0Hz, 2H), 8.55 (s, 2H), 8.21 (s, 1H), 7.97-7.83 (m, 3H), 7.80-7.55 (m, 7H), 7.44 (d, J=20.0Hz, 2H), 7.23 (s, 2H), 7.04 (d, J=32.4Hz, 2H), 2.58 (s, 3H)
The synthesis of 6. compound A6 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C6, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.6g, yield 46.7%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 2H), 8.24 (d, J=21.6Hz, 2H), 7.73-7.29 (m, 17H), 7.13 (d, J=20.0Hz, 4H)
The synthesis of 7. compound A7 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C7, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.9g, yield 65.6%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.55 (s, 2H), 8.24 (d, J =28.0Hz, 5H), 7.57 (ddd, J=44.0,16.0,10.0Hz, 11H), 7.25-7.03 (m, 5H)
The synthesis of 8. compound A-28 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C8, passes through the synthesis of two-step reaction, purifying Obtain white solid 11.5g, yield 74.3%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.28-8.14 (m, 3H), 7.96-7.31 (m, 19H)
The synthesis of 9. compound A9 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C9, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.4g, yield 82.4%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.45 (s, 1H), 8.32 (s, 1H), 8.21 (s, 1H), 7.97 (s, 1H), 7.87 (d, J=4.0Hz, 2H), 7.80-7.47 (m, 12H), 7.47-7.15 (m, 7H)
The synthesis of 10. compound A10 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C10, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.0g, yield 75.4%.
1H NMR (400MHz, Chloroform) δ 8.95 (s, 1H), 8.88 (s, 2H), 8.75 (s, 4H), 8.50 (s, 1H), 8.37 (s, 1H), 8.25 (t, J=14.0Hz, 6H), 8.12-7.94 (m, 3H), 7.88 (d, J=8.0Hz, 2H), 7.81-7.60 (m, 5H), 7.59-7.25 (m, 9H)
The synthesis of 11. compound A11 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C11, passes through the synthesis of two-step reaction, purifying Obtain white solid 7.3g, yield 67.9%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 2H), 8.28-8.12 (m, 4H), 7.73-7.33 (m, 13H), 7.16 (dd, J=22.0,14.0Hz, 6H)
The synthesis of 12. compound A12 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C12, passes through the synthesis of two-step reaction, purifying Obtain white solid, yield 72.8%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 2H), 9.14 (s, 2H), 8.55 (s, 3H), 8.39 (s, 1H), 8.34 (s, 1H), 8.21 (s, 1H), 8.18 (s, 1H), 7.83-7.56 (m, 8H), 7.56-7.34 (m, 5H), 7.29- 7.05 (m, 8H), 1.69 (s, 6H)
The synthesis of 13. compound A13 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C13, passes through the synthesis of two-step reaction, purifying Obtain white solid 15.4g, yield 76.1%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (t, J=3.0Hz, 1H), 9.14 (s, 2H), 8.95 (s, 2H), 8.53 (d, J=20.0Hz, 4H), 8.21 (d, J=3.3Hz, 3H), 7.88 (d, J= 8.0Hz, 3H), 7.83-7.16 (m, 18H)
The synthesis of 14. compound A14 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C14, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.6g, yield 69.8%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 1H), 8.31 (s, 1H), 8.21 (t, J=5.3Hz, 3H), 7.94-7.24 (m, 22H), 7.14 (d, J=20.0Hz, 2H).
The synthesis of 15. compound A15 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C15, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 67.8%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.77 (s, 2H), 8.75 (s, 2H), 8.67 (s, 1H), 8.28 (s, 4H), 8.21 (s, 1H), 8.08 (s, 2H), 7.90 (s, 1H), 7.75 (s, 4H), 7.62 (d, J=20.0Hz, 3H), 7.50-7.33 (m, 6H), 2.50 (s, 6H)
The synthesis of 16. compound A16 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C16, passes through the synthesis of two-step reaction, purifying Obtain white solid 11.4g, yield 68.4%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.18 (s, 1H), 9.14 (s, 2H), 8.55 (s, 2H), 8.22 (t, J=6.0Hz, 3H), 8.16 (s, 1H), 7.80-7.16 (m, 12H), 7.05 (s, 1H), 2.87 (s, 1H), 1.69 (s, 6H), 1.17 (s, 6H)
The synthesis of 17. compound A17 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C17, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.6g, yield 12.5%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 2H), 8.31 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.72-7.33 (m, 13H), 7.16 (dd, J=22.0, 14.0Hz, 6H)
The synthesis of 18. compound A18 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C18, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 57.5%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.26 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.87 (s, 1H), 7.81-7.64 (m, 4H), 7.64-7.36 (m, 7H), 7.35-7.05 (m, 8H), 6.91 (s, 1H), 2.58 (s, 3H)
The synthesis of 19. compound A19 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C19, passes through the synthesis of two-step reaction, purifying Obtain white solid 13.9g, yield 64.2%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (t, J=3.4Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.42 (s, 2H), 8.21 (s, 1H), 8.10 (s, 2H), 7.81-7.31 (m, 15H), 7.17 (t, J=24.0Hz, 4H)
The synthesis of 20. compound A20 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C20, passes through the synthesis of two-step reaction, purifying Obtain white solid 15.8g, yield 69.5%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.95 (s, 1H), 8.88 (s, 2H), 8.71 (d, J =8.0Hz, 4H), 8.53 (d, J=20.0Hz, 2H), 8.20 (d, J=8.2Hz, 2H), 7.98 (s, 1H), 7.89 (s, 1H), 7.78 (d, J=4.0Hz, 2H), 7.73-7.25 (m, 11H), 7.13 (d, J=20.0Hz, 2H)
The synthesis of 21. compound A21 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C21, passes through the synthesis of two-step reaction, purifying Obtain white solid 12.5g, yield 65.3%.
1H NMR (400MHz, Chloroform) δ 9.34 (s, 1H), 8.88 (s, 2H), 8.77 (d, J=16.0Hz, 5H), 8.55 (s, 1H), 8.42-8.15 (m, 10H), 7.77-7.42 (m, 11H), 7.13 (d, J=20.0Hz, 2H)
The synthesis of 22. compound A22 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C22, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.5g, yield 56.2%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.15 (d, J=8.0Hz, 4H), 8.55 (d, J=0.5Hz, 3H), 8.37 (s, 1H), 8.21 (s, 1H), 8.17-7.40 (m, 13H), 7.21 (d, J=17.8Hz, 3H), 2.44 (s, 3H)
The synthesis of 23. compound A23 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C23, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.65g, yield 55.4%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.51 (s, 1H), 8.24-8.06 (m, 4H), 7.83-7.32 (m, 14H), 7.08 (s, 1H)
The synthesis of 24. compound A24 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C24, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.95g, yield 59.1%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 1H), 9.16 (t, J=3.3Hz, 1H), 9.14 (s, 2H), 8.95 (s, 1H), 8.53 (d, J=20.0Hz, 3H), 8.36 (s, 1H), 8.30-8.17 (m, 4H), 7.88 (d, J=8.0Hz, 2H), 7.81-7.13 (m, 15H), 1.69 (s, 6H)
The synthesis of 25. compound A25 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C25, passes through the synthesis of two-step reaction, purifying Obtain white solid 7.66g, yield 48.3%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.35- 8.19 (m, 7H), 7.87 (s, 1H), 7.79-7.38 (m, 16H), 7.25 (s, 8H)
The synthesis of 26. compound A26 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C26, passes through the synthesis of two-step reaction, purifying Obtain white solid 6.59g, yield 46.8%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.55 (s, 2H), 8.28 (s, 4H), 8.21 (s, 1H), 7.91 (d, J=4.0Hz, 4H), 7.75 (s, 2H), 7.67- 7.34 (m, 9H), 7.22-7.03 (m, 5H).
The synthesis of 27. compound A27 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C27, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.72g, yield 60.3%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.18 (s, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.33 (s, 1H), 8.22 (d, J=12.0Hz, 2H), 8.18 (s, 1H), 7.82-7.04 (m, 14H)
The synthesis of 28. compound A28 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C28, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.33g, yield 72.1%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.75 (s, 4H), 8.55 (s, 1H), 8.28 (s, 2H), 8.28-8.13 (m, 5H), 7.79 (s, 1H), 7.72-7.42 (m, 9H), 7.33-6.96 (m, 8H), 1.33 (s, 9H)
The synthesis of 29. compound A29 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C29, passes through the synthesis of two-step reaction, purifying Obtain white solid 13.0g, yield 75.4%.
1H NMR (400MHz, Chloroform) δ 8.95 (s, 1H), 8.88 (s, 2H), 8.75 (s, 4H), 8.50 (s, 1H), 8.37 (s, 1H), 8.25 (t, J=14.0Hz, 6H), 8.12-7.94 (m, 3H), 7.88 (d, J=8.0Hz, 2H), 7.81-7.60 (m, 5H), 7.59-7.25 (m, 9H)
The synthesis of 30. compound A-13 0 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C30, passes through the synthesis of two-step reaction, purifying Obtain white solid 14.3g, yield 67.9%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 2H), 8.28-8.12 (m, 4H), 7.73-7.33 (m, 13H), 7.16 (dd, J=22.0,14.0Hz, 6H)
The synthesis of 31. compound A-13 1 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C31, passes through the synthesis of two-step reaction, purifying Obtain white solid 13.5g, yield 72.8%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 2H), 9.14 (s, 2H), 8.55 (s, 3H), 8.39 (s, 1H), 8.34 (s, 1H), 8.21 (s, 1H), 8.18 (s, 1H), 7.83-7.56 (m, 8H), 7.56-7.34 (m, 5H), 7.29- 7.05 (m, 8H), 1.69 (s, 6H)
The synthesis of 32. compound A-13 2 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C32, passes through the synthesis of two-step reaction, purifying Obtain white solid 15.4g, yield 76.1%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (t, J=3.0Hz, 1H), 9.14 (s, 2H), 8.95 (s, 2H), 8.53 (d, J=20.0Hz, 4H), 8.21 (d, J=3.3Hz, 3H), 7.88 (d, J= 8.0Hz, 3H), 7.83-7.16 (m, 18H)
The synthesis of 33. compound A-13 3 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C33, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.6g, yield 69.8%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 1H), 8.31 (s, 1H), 8.21 (t, J=5.3Hz, 3H), 7.94-7.24 (m, 22H), 7.14 (d, J=20.0Hz, 2H).
The synthesis of 34. compound A-13 4 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C34, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 67.8%.
1H NMR (400MHz, Chloroform) δ 8.88 (s, 2H), 8.77 (s, 2H), 8.75 (s, 2H), 8.67 (s, 1H), 8.28 (s, 4H), 8.21 (s, 1H), 8.08 (s, 2H), 7.90 (s, 1H), 7.75 (s, 4H), 7.62 (d, J=20.0Hz, 3H), 7.50-7.33 (m, 6H), 2.50 (s, 6H)
The synthesis of 35. compound A-13 5 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C35, passes through the synthesis of two-step reaction, purifying Obtain white solid 11.4g, yield 68.4%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.18 (s, 1H), 9.14 (s, 2H), 8.55 (s, 2H), 8.22 (t, J=6.0Hz, 3H), 8.16 (s, 1H), 7.80-7.16 (m, 12H), 7.05 (s, 1H), 2.87 (s, 1H), 1.69 (s, 6H), 1.17 (s, 6H)
The synthesis of 36. compound A-13 6 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C36, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.6g, yield 12.5%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 2H), 8.31 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.72-7.33 (m, 13H), 7.16 (dd, J=22.0, 14.0Hz, 6H)
The synthesis of 37. compound A-13 7 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C37, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 57.5%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.26 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.87 (s, 1H), 7.81-7.64 (m, 4H), 7.64-7.36 (m, 7H), 7.35-7.05 (m, 8H), 6.91 (s, 1H), 2.58 (s, 3H)
The synthesis of 38. compound A-13 8 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C38, passes through the synthesis of two-step reaction, purifying Obtain white solid 13.9g, yield 64.2%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (t, J=3.4Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.42 (s, 2H), 8.21 (s, 1H), 8.10 (s, 2H), 7.81-7.31 (m, 15H), 7.17 (t, J=24.0Hz, 4H)
The synthesis of 39. compound A-13 9 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C39, passes through the synthesis of two-step reaction, purifying Obtain white solid 15.8g, yield 69.5%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.95 (s, 1H), 8.88 (s, 2H), 8.71 (d, J =8.0Hz, 4H), 8.53 (d, J=20.0Hz, 2H), 8.20 (d, J=8.2Hz, 2H), 7.98 (s, 1H), 7.89 (s, 1H), 7.78 (d, J=4.0Hz, 2H), 7.73-7.25 (m, 11H), 7.13 (d, J=20.0Hz, 2H)
The synthesis of 40. compound A40 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C40, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.5g, yield 56.2%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.15 (d, J=8.0Hz, 4H), 8.55 (d, J=0.5Hz, 3H), 8.37 (s, 1H), 8.21 (s, 1H), 8.17-7.40 (m, 13H), 7.21 (d, J=17.8Hz, 3H), 2.44 (s, 3H)
The synthesis of 41. compound A41 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C41, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.5g, yield 56.2%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.15 (d, J=8.0Hz, 4H), 8.55 (d, J=0.5Hz, 3H), 8.37 (s, 1H), 8.21 (s, 1H), 8.17-7.40 (m, 13H), 7.21 (d, J=17.8Hz, 3H), 2.44 (s, 3H)
The synthesis of 42. compound A42 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C42, passes through the synthesis of two-step reaction, purifying Obtain white solid 11.4g, yield 68.4%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.18 (s, 1H), 9.14 (s, 2H), 8.55 (s, 2H), 8.22 (t, J=6.0Hz, 3H), 8.16 (s, 1H), 7.80-7.16 (m, 12H), 7.05 (s, 1H), 2.87 (s, 1H), 1.69 (s, 6H), 1.17 (s, 6H)
The synthesis of 43. compound A43 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C43, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.6g, yield 69.8%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.55 (s, 1H), 8.31 (s, 1H), 8.21 (t, J=5.3Hz, 3H), 7.94-7.24 (m, 22H), 7.14 (d, J=20.0Hz, 2H).
The synthesis of 44. compound A44 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C44, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 57.5%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.26 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.87 (s, 1H), 7.81-7.64 (m, 4H), 7.64-7.36 (m, 7H), 7.35-7.05 (m, 8H), 6.91 (s, 1H), 2.58 (s, 3H)
The synthesis of 45. compound A45 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C45, passes through the synthesis of two-step reaction, purifying Obtain white solid 9.65g, yield 55.4%.
1H NMR (400MHz, Chloroform) δ 9.63 (s, 2H), 8.88 (s, 2H), 8.71 (d, J=8.0Hz, 4H), 8.51 (s, 1H), 8.24-8.06 (m, 4H), 7.83-7.32 (m, 14H), 7.08 (s, 1H)
The synthesis of 46. compound A46 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C46, passes through the synthesis of two-step reaction, purifying Obtain white solid 10.4g, yield 57.5%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (d, J=2.9Hz, 1H), 9.14 (s, 2H), 8.55 (s, 3H), 8.26 (s, 1H), 8.20 (d, J=8.0Hz, 3H), 7.87 (s, 1H), 7.81-7.64 (m, 4H), 7.64-7.36 (m, 7H), 7.35-7.05 (m, 8H), 6.91 (s, 1H), 2.58 (s, 3H)
The synthesis of 47. compound 47 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C47, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.9g, yield 60.5%.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 2H), 8.88 (d, J=32.0Hz, 2H), 8.55 (s, 2H), 8.21 (s, 1H), 7.97-7.83 (m, 3H), 7.80-7.55 (m, 7H), 7.44 (d, J=20.0Hz, 2H), 7.23 (s, 2H), 7.04 (d, J=32.4Hz, 2H), 2.58 (s, 3H)
The synthesis of 48. compound A48 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C48, passes through the synthesis of two-step reaction, purifying Obtain white solid 15.4g, yield 76.1%.
1H NMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.16 (t, J=3.0Hz, 1H), 9.14 (s, 2H), 8.95 (s, 2H), 8.53 (d, J=20.0Hz, 4H), 8.21 (d, J=3.3Hz, 3H), 7.88 (d, J= 8.0Hz, 3H), 7.83-7.16 (m, 18H)
The synthesis of 49. compound A49 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C49, passes through the synthesis of two-step reaction, purifying Obtain white solid 8.0g, yield 75.4%.
1H NMR (400MHz, Chloroform) δ 8.95 (s, 1H), 8.88 (s, 2H), 8.75 (s, 4H), 8.50 (s, 1H), 8.37 (s, 1H), 8.25 (t, J=14.0Hz, 6H), 8.12-7.94 (m, 3H), 7.88 (d, J=8.0Hz, 2H), 7.81-7.60 (m, 5H), 7.59-7.25 (m, 9H)
The synthesis of 50. compound A-45 0 of synthetic example
Synthesis step is with compound A1, the difference is that C1 is replaced with C50, passes through the synthesis of two-step reaction, purifying Obtain white solid 11.4g, yield 68.4%.
1HNMR (400MHz, Chloroform) δ 9.20 (d, J=3.1Hz, 1H), 9.18 (s, 1H), 9.14 (s, 2H), 8.55 (s, 2H), 8.22 (t, J=6.0Hz, 3H), 8.16 (s, 1H), 7.80-7.16 (m, 12H), 7.05 (s, 1H), 2.87 (s, 1H), 1.69 (s, 6H), 1.17 (s, 6H)
The analysis detecting data of specific preferred compound disclosed in the embodiment of the present invention arranges in table 1 below:
Table 1
Device embodiments:
Organic Light Emitting Diode includes the first electrode and second electrode on substrate, and between electrode Organic material includes hole transmission layer, luminescent layer, electron transfer layer between first electrode and second electrode.
Substrate using substrate used in organic light emitting display, such as: glass, polymer material and have TFT member device Glass and polymer material of part etc..
Anode material can use indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide (ZnO) etc. Transparent conductive material is also possible to the metal materials such as silver and its alloy, aluminium and its alloy, is also possible to the organic conductives such as PEDOT The multilayered structure of material and above-mentioned material.
Cathode is metals, metal mixture, the oxide such as magnesium silver mixture, LiF/A1, ITO.
It can also include hole transmission layer, the hole injection layer between luminescent layer and anode in device, these layers can To be but not limited to the combination of one or more compounds of following enumerated HT1-HT31.
Device luminescent layer may include material of main part and luminescent dye, wherein fluorescent host can be but not limited to following The one or more combinations for the BFH1-BFH14 enumerated.
Luminescent dye can be but not limited to one or more combinations of following enumerated BFD1-BFD9.
The organic material layer may include electron transfer layer, and the hole between luminescent layer and electron transfer layer Barrier layer.Hole blocking layer and electron transport layer materials can be but not limited to following enumerated ET1-ET57 one kind or A variety of combinations.
It can also include the electron injecting layer between electron transfer layer and cathode, electron injecting layer material in device The including but not limited to following one or more combinations enumerated:
LiQ, LiF, NaC1, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.
The organic electroluminescence device preparation process of device embodiments and device comparative example of the present invention is as follows, in device reality It applies in example 1~12, the compounds of this invention is used as electron transport material.
Device comparative example 1
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, is rushed in deionized water It washes, in acetone: ultrasonic oil removing in alcohol mixed solvent is baked under clean environment and completely removes moisture content, with ultraviolet light and smelly Oxygen cleaning, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to pressure less than 10-5Pa, in above-mentioned sun Vacuum evaporation HT-2 is as hole injection layer on the tunic of pole, and evaporation rate 0.1nm/s, vapor deposition film thickness is 10nm；
Hole transmission layer of the vacuum evaporation HT-6 as device on hole injection layer, evaporation rate 0.1nm/s, Vapor deposition total film thickness is 80nm；
The luminescent layer of vacuum evaporation device on hole transmission layer, luminescent layer include material of main part and dye materials, benefit The method steamed altogether with multi-source, adjusting material of main part BFH-8 evaporation rate are 0.1nm/s, set the evaporation rate of dyestuff BFD-1 Based on material evaporation rate 3%, vapor deposition total film thickness be 30 nm；
The electron transport layer materials ET-1 of vacuum evaporation device, evaporation rate 0.1nm/s on luminescent layer steam Plating total film thickness is 30nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of Cathode of the Al layer of 150nm as device.
Device embodiments 1
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A1.
Device embodiments 2
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A2.
Device embodiments 3
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A4.
Device embodiments 4
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A7.
Device embodiments 5
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A11.
Device embodiments 6
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A16.
Device embodiments 7
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A19.
Device embodiments 8
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A23.
Device embodiments 9
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A24.
Device embodiments 10
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A-13 1.
Device embodiments 11
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A43.
Device embodiments 12
Organic electroluminescence device is prepared using method identical with device comparative example 1, the difference is that, it will ET-1 replaces with compound A-45 2.
Following performance measurement is carried out to the organic electroluminescence device prepared by the above process:
Under same brightness, the 750 type photoradiometer ST-86LA type luminance meter of PR of Photo Research company is used It is made in (photoelectric instrument factory, Beijing Normal University) and Keithley4200 test macro measurement Examples 1 to 9 and comparative example 1 The driving voltage of standby obtained organic electroluminescence device and the service life of current efficiency and device.Specifically, with per second The rate of 0.1V promotes voltage, and measurement reaches 1000cd/m when the brightness of organic electroluminescence device2When voltage drive electricity Pressure, while measuring current density at this time；The ratio of brightness and current density is current efficiency；The life test of LT95 is such as Under: using luminance meter in 1000cd/m2Under brightness, the electric current kept constant, the brightness for measuring organic electroluminescence device is reduced to 950cd/m2Time, unit is hour.
Apply the organic electroluminescence device of concrete preferred structure compound disclosed in synthetic example of the present invention See Table 2 for details for performance detection data.
Table 2
Device embodiments 1~1 2 are compared with device comparative example l, the other materials phase in organic electroluminescence device structure With in the case where, series compound of the present invention is used to replace in device comparative example 1 ET-1 as electron transport layer materials, as a result device The driving voltage of part has apparent reduction, and current efficiency, which has, obviously to be promoted, and material of the invention is compared with Example compared in mutually isostructural device its service life have and be extremely obviously improved.This is because there is no the present invention in ET-1 Phenanthro- pyrimidine group in compound, conjugated system is smaller and is unfavorable for the injection of electronics, therefore driving voltage is higher, the service life It is shorter.
The above result shows that new organic materials of the invention are used for organic electroluminescence device, can effectively drop Low landing voltage improves current efficiency, it is seen that new organic materials of the invention are electron transport layer materials of good performance.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail, within the scope of the technical concept of the present invention, can with various simple variants of the technical solution of the present invention are made, These simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance It in the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention is to various No further explanation will be given for possible combination.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (11)

1. a kind of organic compound is indicated by leading to formula (I) as follows:
Wherein, Ar1Substituted or unsubstituted aryl selected from C6~C60；Ar2Substituted or unsubstituted virtue selected from C6~C60 The heteroaryl of base, C6~C30 containing pyridine groups；
L1、L2The separately arlydene selected from singly-bound, C6~C14；
R1~R9Separately it is selected from the substituted or unsubstituted virtue of hydrogen, halogen, cyano, the alkyl of C1~C12, C6~C30 The substituted or unsubstituted heteroaryl of base, C3~C30；
When the aryl or heteroaryl have substituent group, which is selected from the aryl of the alkyl of C1~C8, C6~C30.
2. organic compound according to claim 1 is indicated by leading to formula (II) as follows:
Wherein, Ar1Substituted or unsubstituted aryl selected from C6~C40；Ar2Substituted or unsubstituted virtue selected from C6~C40 The heteroaryl of base, C6~C30 containing pyridine groups；
L1、L2Separately it is selected from singly-bound, phenylene, naphthylene；
R9Selected from methyl, ethyl, cyclohexyl, phenyl, naphthalene；
When the aryl or heteroaryl have substituent group, which is selected from the aryl of the alkyl of C1~C8, C6~C30.
3. organic compound according to claim 1 is indicated by leading to formula (III) as follows:
Wherein, Ar1Substituted or unsubstituted aryl selected from C6~C20；Ar2Substituted or unsubstituted virtue selected from C6~C20 The heteroaryl of base, C6~C16 containing pyridine groups；
L2Selected from singly-bound, phenylene, naphthylene；
When the aryl or heteroaryl have substituent group, which is selected from the aryl of the alkyl of C1~C8, C6~C24.
4. organic compound according to claim 1, wherein R1~R8Separately it is selected from hydrogen, halogen, cyano, first Base, ethyl, propyl, phenyl, naphthalene are preferably selected from hydrogen, chlorine, cyano, methyl, ethyl, most preferably hydrogen.
5. organic compound according to any one of claims 1 to 4, wherein Ar2Selected from phenyl, naphthalene, pyridyl group, connection Pyridyl group, phenylpyridyl, naphthlypyridine base, phenyl napthyl pyridyl group, naphthylphenyl pyridyl group, xenyl pyridyl group, pyridine Base phenylpyridyl, pyridyl group naphthlypyridine base, quinolyl pyridyl group.
6. organic compound according to any one of claims 1 to 4, wherein Ar2For one of following group:
7. organic compound according to claim 1 or 2, wherein Ar1Selected from phenyl, anthryl, phenanthryl, fluoranthene base, base, Xenyl, terphenyl, benzene binaphthyl, naphthalene xenyl, biphenyl dianthranide base, binaphthyl, triphenylene (9,10- benzophenanthrene), 9, It is 9- dimethyl fluorenyl, Spirofluorene-based.
8. organic compound described in any one of claim 1 to 3 is one of following compound A1~A78:
9. application of the organic compound described in claim 1~8 in organic electroluminescence device.
10. a kind of organic electroluminescence device, including first electrode, second electrode and it is inserted in the first electrode and the second electricity If the dried organic layer between pole, which is characterized in that contain the organic compound described in claim 1~8 in the organic layer.
11. organic electroluminescence device according to claim 10, the organic compound is used as electron transport layer materials, electricity Son injection layer material or emitting layer material.
CN201810440684.5A 2018-05-09 2018-05-09 Phenanthro- pyrimidine derivatives and its application in an organic light emitting device Pending CN110467577A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113480393A (en) * 2021-06-16 2021-10-08 湖南大学 Method for preparing functionalized polysubstituted aromatic hydrocarbon through series reaction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113480393A (en) * 2021-06-16 2021-10-08 湖南大学 Method for preparing functionalized polysubstituted aromatic hydrocarbon through series reaction

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Application publication date: 20191119