CN103113281A - Benzanthracene efficient organic light emitting material and preparation method - Google Patents
Benzanthracene efficient organic light emitting material and preparation method Download PDFInfo
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- CN103113281A CN103113281A CN201210455526XA CN201210455526A CN103113281A CN 103113281 A CN103113281 A CN 103113281A CN 201210455526X A CN201210455526X A CN 201210455526XA CN 201210455526 A CN201210455526 A CN 201210455526A CN 103113281 A CN103113281 A CN 103113281A
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Abstract
The invention provides a benzanthracene efficient organic light emitting material. The benzanthracene efficient organic light emitting material has the structural formula shown as follows, wherein A group is the substituted or unsubstituted annular aryl group with 6 to 30 carbons. The benzanthracene efficient organic light emitting material is simple in synthetic method, low in cost, easy to purify, high in yield, and remarkable in light emitting efficiency, luminance, driving voltage, service life and stability, can be manufactured into a component of a display well in order to realize application, and also can be used for adjusting a light emitting peak position.
Description
Technical field
The present invention relates to the organic photoelectrical material field, relate in particular to the electroluminescent organic material that contains novel Benzanthracenes derivative.
Background technology
The organic electroluminescent technology is the latest generation flat panel display, can be used for flat-panel monitor and lighting source, and present commercial flat-panel monitor puts goods on the market.Lighting source is because the absolute predominance of himself is also very fast with industrialization.Electroluminescent device has structure of whole solid state, and electroluminescent organic material is core and the basis that consists of this device.The exploitation of novel material is to promote the constantly driving source of progress of electroluminescent technology.Also the study hotspot of present organic electroluminescent industry to original material preparation and device optimization.
At present to the OLED(organic electroluminescence device) exploitation obtained very huge development, but the progress along with application and development, requirement to material is also more and more higher, more particularly can carry dynamical luminous organic material, because synthetic technology is more difficult now, purification difficult, the building-up process of some compound may also relate to more virose raw material or the course of processing, makes OLED make slow progress aspect industrialized development.
The OLED phenomenon is from discovery monocrystalline anthracene is luminous, OLED has caused the upsurge of scientific research, people also experience the overwhelming majority in the exploitation that has been placed on the anthracene structural derivative and go simultaneously, have developed the electroluminescent organic material system of many series now, obtain certain effect.Mainly concentrate on three arylamine systems, anthracene derivative, carbazole derivative, some classical compound systems such as metal complexes, what now a lot of OLED industrialization developments also all adopted is these basic structures.But current material also exists the difficult problem of application, such as the life-span, and brightness, all there is certain problem in efficient etc., and material how to develop excellent property is exactly the utmost point when business.
Summary of the invention
The purpose of this invention is to provide a kind of convenient operation, easily purify, productive rate is high, the luminous organic material that cost is low, due to this series luminous organic material in luminous efficiency, brightness, driving voltage, there is good performance life-span and stable aspect, and therefore reasonable using value is arranged in organic luminescent device.
For achieving the above object, the invention provides the efficient luminous organic material of a kind of Benzanthracenes, it is characterized in that general formula is as the formula (1):
Wherein the A group is for replacing or being the aryl of 6-30 without the carbon number of the formation ring that replaces, and concrete structure is as follows:
Wherein-be the site that is connected with phenyl ring.
The specific examples of the new Organic Electro Luminescent Materials of formula of the present invention (1) expression is as follows, but is not limited to these given compounds of following instance:
Above is exactly concrete structure formation, but this series compound is not limited to these listed chemical structures.Every take structural formula (1) as the basis, the arbitrary structures of the concrete structure that provides before the A group is respectively, the compound of these groups of every these groups and replacement thereof and the simple transformation of the position of substitution all should be included.
The present invention also provides the synthetic route of the luminous organic material of the above-mentioned novel texture of having optimized, and has provided the preparation method.To contain the Benzanthracenes bromo-derivative of fluorenyl replacement and the boric acid of different substituents and obtain structural formula (1) compounds by the Suzuki linked reaction.
The described preparation method who contains the Benzanthracenes derivative, wherein, described step specifically comprises the following steps:
The Benzanthracenes bromo-derivative of fluorenyl replacement, boric acid, alkali and the solvent of different substituents are added reaction flask, utilize nitrogen bubble degassed to reaction system, add catalyzer, be warming up to 70-100 ℃, reacted 15-30 hour;
In described step, 3-(4-bromonaphthalene base)-7, the mol ratio of the boric acid of 7-dimethyl-7H-benzanthrene and different substituents is 1:1.5 ~ 2.0.Described solvent is organic solvent and water.Described organic solvent can be selected tetrahydrofuran (THF), toluene or dimethylbenzene, and the volume ratio of organic solvent and water is 2:1.Described catalyzer is preferably four (triphenyl phosphorus) palladium, catalyzer and 3-(4-bromonaphthalene base)-mol ratio of 7,7-dimethyl-7H-benzanthrene is 1:50 ~ 100.Described alkali is preferably sodium carbonate, sodium carbonate and 3-(4-bromonaphthalene base)-mol ratio of 7,7-dimethyl-7H-benzanthrene is 2 ~ 4:1.
The synthetic aftertreatment of described structural formula (1) compounds mainly comprises suction filtration, washing and oven dry.
Embodiment
Embodiment 1: compound 001 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g(50mmol with the fluorenyl replacement), N-phenyl carbazole ylboronic acid 21.69g(75mmol), sodium carbonate 10.60g(100mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 0.58g(0.5mmol), be warming up to 70 ℃, reacted 15 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 34.13g, productive rate is more than 93%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 733.89; Test value is 733.88.Ultimate analysis: calculated value is C:93.28%; H:4.81%; N:1.91%; Test value is C:93.28%; H:4.82%; N:1.90%.
Embodiment 2: compound 002 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g(50mmol with the fluorenyl replacement), coffee Luo Lin ylboronic acid 17.92g(80mmol), sodium carbonate 12.19g (115mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 0.69g (0.6mmol), be warming up to 80 ℃, reacted 17 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 31.19g, productive rate is more than 93%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 670.80; Test value is 670.78.Ultimate analysis: calculated value is C:91.32%; H:4.51%; N:4.18%; Test value is C:91.31%; H:4.53%; N:4.19%.
Embodiment 3: compound 003 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g(50mmol with the fluorenyl replacement), 2-first base benzoxazole ylboronic acid 15.04g(85mmol), sodium carbonate 13.78g(130mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 0.81g(0.7mmol), be warming up to 85 ℃, reacted 19 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 29.31g, productive rate is more than 94%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 623.74; Test value is 623.72.Ultimate analysis: calculated value is C:90.50%; H:4.69%; N:2.25%; O:2.57%; Test value is C:90.48%; H:4.70%; N:2.26%; O:2.57%.
Embodiment 4: compound 004 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g(50mmol with the fluorenyl replacement) perylene ylboronic acid 26.83g(90mmol), sodium carbonate 15.9g(150mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 0.92g(0.8mmol), be warming up to 90 ℃, reacted 21 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 33.80g, productive rate is more than 91%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 742.90; Test value is 742.92.Ultimate analysis: calculated value is C:95.39%; H:4.61%; Test value is C:95.40%; H:4.60%.
Embodiment 5: compound 005 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g(50mmol with the fluorenyl replacement), indenyl boric acid 16.00g(95mmol), sodium carbonate 18.55g (175mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 1.04g (0.9mmol), be warming up to backflow, reacted 24 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 28.52g, productive rate is more than 94%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is that 606.75 test values are 606.73.Ultimate analysis: calculated value is C:95.02%; H:4.98%; Test value is C:95.04%; H:5.00%.
Embodiment 6: compound 006 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 28.58g (50mmol) with the fluorenyl replacement, fluorenyl boric acid 21.00g (100mmol), sodium carbonate 21.10g (200mmol), tetrahydrofuran (THF) 250ml and water 125ml add there-necked flask, degassed, add four (triphenyl phosphorus) palladium 1.16g (1.0mmol), be warming up to 100 ℃, reacted 30 hours, be cooled to room temperature, after separating out solid, suction filtration, filter cake through washing, ethanol is washed wash with ether after, oven dry obtains asymmetric Benzanthracenes derivative 30.87g, productive rate is more than 94%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 656.81; Test value is 656.83.Ultimate analysis: calculated value is C:95.09%; H:4.91%; Test value is C:95.07%; H:4.93%.
The application implementation case
With its ito glass substrate that is formed with 1000 thickness in the above, be placed on the ultrasonic middle cleaning 30 minutes of washings, then use the distilled water ultrasonic cleaning 10 minutes twice.After distilled water wash is complete, use respectively Virahol, toluene, acetone, ethanol difference ultrasonic cleaning 30 minutes, then dry.Put at last the plasma washing machine, use oxygen plasma cleaning base plate 5 minutes, send into vacuum evaporation equipment and process.
With NPB, synthetic materials, AlQ, LiF, Al evaporation respectively to device, go into the object construction device: [ITO/NPB (20nm)/001(30nm)/AlQ (20nm)/LiF (5nm)/Al (10nm)], velocity of evaporation is that organism is 1/s, the velocity of evaporation of LiF is 0.5/s, and the velocity of evaporation of Al is 2/s, and vacuum keep is 10
-5The vacuum tightness that the pa normal atmosphere is following.
The test result of device 001 is cut-in voltage 4v, and high-high brightness is 3500cd/m
2, observing efficient under 10v voltage is 26Lm/w, chromaticity coordinates (CIE) value is x:0.14; Y:0.16 obtains a blue device, and life-span transformation period of device is 20000h.
The luminous efficiency of gained compound in table 1 embodiment
Can find out from above-mentioned data, in embodiment, novel electroluminescent organic material has high luminous efficiency, and high luminous efficiency shows that this compound can be used as luminescent material or luminous material of main part and transport material, is applied in electroluminescent device.Simultaneously according to application example 1, we are applied to material in organic electroluminescence device, by data test and comparison, we find electroluminescent organic material, particularly Performance Ratio that this class material is excellent property luminous material of main part and transport material preferably really.It is a very promising class electroluminescent organic material.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (4)
1. efficient luminous organic material of Benzanthracenes is characterized in that general formula is as the formula (1):
Wherein the A group is for replacing or being the aryl of 6-30 without the carbon number of the formation ring that replaces, and concrete structure is as follows:
Wherein-be the site that is connected with phenyl ring.
2. the efficient luminous organic material of Benzanthracenes according to claim 1 is characterized in that: the compound that comprises lower array structure:
。
3. according to claim 1, the preparation method of the 2 efficient luminous organic materials of described Benzanthracenes, it is characterized in that comprising the following steps:
The Benzanthracenes bromo-derivative of fluorenyl replacement, boric acid, alkali and the solvent of different substituents are added reaction flask, utilize nitrogen bubble degassed to reaction system, add catalyzer, be warming up to 70-100 ℃, reacted 15-30 hour;
in described step, the mol ratio of the Benzanthracenes bromo-derivative that fluorenyl replaces and the boric acid of different substituents is 1:1.5 ~ 2.0, described solvent is organic solvent and water, described organic solvent can be selected tetrahydrofuran (THF), toluene or dimethylbenzene etc., the volume ratio of organic solvent and water is 2:1, described catalyzer is preferably four (triphenyl phosphorus) palladium, the mol ratio of the Benzanthracenes bromo-derivative that catalyzer and fluorenyl replace is 1:50 ~ 100, described alkali is preferably sodium carbonate, the mol ratio of the Benzanthracenes bromo-derivative that sodium carbonate and fluorenyl replace is 2 ~ 4:1, the compou nd synthesis aftertreatment mainly comprises suction filtration, washing and oven dry.
4. the preparation method of the efficient luminous organic material of Benzanthracenes according to claim 3, it is characterized in that: it is characterized in that: the mol ratio of the Benzanthracenes bromo-derivative that fluorenyl replaces and the boric acid of different substituents is 1:1.8, described organic solvent is selected tetrahydrofuran (THF), the volume ratio of tetrahydrofuran (THF) and water is 2:1, described catalyzer is preferably four (triphenyl phosphorus) palladium, the mol ratio of the Benzanthracenes bromo-derivative that catalyzer and fluorenyl replace is 1:62.5, described alkali is preferably sodium carbonate, and the mol ratio of the Benzanthracenes bromo-derivative that sodium carbonate and fluorenyl replace is 3:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105523991B (en) * | 2015-12-22 | 2018-05-01 | 吉林奥来德光电材料股份有限公司 | A kind of new carbazole compound and its preparation method and application |
| CN108047130A (en) * | 2017-12-05 | 2018-05-18 | 李现伟 | Benzanthracenes electroluminescent organic material, luminescent device and display |
| EP3533793A1 (en) * | 2018-02-28 | 2019-09-04 | Novaled GmbH | Organic electronic device, display and lighting devices comprising the same |
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| CN101203582A (en) * | 2005-04-08 | 2008-06-18 | 庄臣及庄臣视力保护公司 | Ophthalmic devices comprising photochromic materials having extended Pi-conjugated systems |
| KR20090011488A (en) * | 2007-07-26 | 2009-02-02 | 대주전자재료 주식회사 | Spiro type organic light emitting materials |
| WO2010038956A2 (en) * | 2008-09-30 | 2010-04-08 | Daejoo Electronic Materials Co., Ltd. | Novel aromatic derivatives and organic electroluminescent device comprising same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101203582A (en) * | 2005-04-08 | 2008-06-18 | 庄臣及庄臣视力保护公司 | Ophthalmic devices comprising photochromic materials having extended Pi-conjugated systems |
| KR20090011488A (en) * | 2007-07-26 | 2009-02-02 | 대주전자재료 주식회사 | Spiro type organic light emitting materials |
| WO2010038956A2 (en) * | 2008-09-30 | 2010-04-08 | Daejoo Electronic Materials Co., Ltd. | Novel aromatic derivatives and organic electroluminescent device comprising same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523991B (en) * | 2015-12-22 | 2018-05-01 | 吉林奥来德光电材料股份有限公司 | A kind of new carbazole compound and its preparation method and application |
| CN108047130A (en) * | 2017-12-05 | 2018-05-18 | 李现伟 | Benzanthracenes electroluminescent organic material, luminescent device and display |
| EP3533793A1 (en) * | 2018-02-28 | 2019-09-04 | Novaled GmbH | Organic electronic device, display and lighting devices comprising the same |
| WO2019166270A1 (en) * | 2018-02-28 | 2019-09-06 | Novaled Gmbh | Organic electronic device, display and lighting devices comprising the same |
| CN111770922A (en) * | 2018-02-28 | 2020-10-13 | 诺瓦尔德股份有限公司 | Organic electronic device, display and lighting apparatus including the same |
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Application publication date: 20130522 |