CN103113289A - Organic electroluminescent material containing benzanthracene derivative and preparation method of organic electroluminescent material - Google Patents
Organic electroluminescent material containing benzanthracene derivative and preparation method of organic electroluminescent material Download PDFInfo
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Abstract
The invention discloses an organic electroluminescent material containing benzanthracene derivative. The structure general formula of the organic electroluminescent material is as shown in the specification. In the structure general formula, a group A is a substituted or unsubstituted aryl used for forming a cycle and provided with 6-30 carbons. The organic electroluminescent material containing benzanthracene derivative disclosed by the invention is simple in synthetic method, low in cost, easy to purify, high in yield and good in performance of luminescent efficiency, luminance, driving voltage, service life and stability; the organic electroluminescent material can be preferably prepared into a display component for use; and luminescence peak positions can be adjusted.
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 a kind of electroluminescent organic material that contains the Benzanthracenes derivative, it is characterized in that general structure is as follows:
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 electroluminescent organic material of the present invention is as follows, but is not limited to these given compounds of following instance:
Above is exactly concrete structure formation, but this series compound does not limit to and these listed chemical structures.Every take structural formula 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 the structural formula 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, 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, and 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, and described alkali is preferably sodium carbonate, and the mol ratio of the Benzanthracenes bromo-derivative that sodium carbonate and fluorenyl replace is 2 ~ 4:1.
The synthetic aftertreatment of described structural formula compounds mainly comprises suction filtration, washing and oven dry.
Beneficial effect of the present invention: can increase solvability by increasing substituting group and substituent different conversion, more easily processing, can be made into better display device and use; Simultaneously also can regulate luminous peak position.
Embodiment
Embodiment 1: compound 001 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(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 27.96g, productive rate is more than 92%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 607.74; Test value is 607.72.Ultimate analysis: calculated value is C:92.89%; H:4.81%; N:2.30%; Test value is C:92.88%; H:4.83%; N:2.31%.
Embodiment 2: compound 002 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(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 25.33g, productive rate is more than 93%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 544.64; Test value is 544.62.Ultimate analysis: calculated value is C:90.42%; H:4.44%; N:5.14%; Test value is C:90.41%; H:4.46%; N:5.15%.
Embodiment 3: compound 003 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(50mmol with the fluorenyl replacement), 2-first base benzoxazole ylboronic acid 15.04 g(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 23.14g, productive rate is more than 93%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 497.58; Test value is 497.56.Ultimate analysis: calculated value is C:89.31%; H:4.66%; N:2.81%; O:3.22%; Test value is C:89.32%; H:4.64%; N:2.83%; O:3.21%.
Embodiment 4: compound 004 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(50mmol with the fluorenyl replacement) perylene ylboronic acid 26.83g(90mmol), sodium carbonate 15.90g(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 28.06g, productive rate is more than 91%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 616.75; Test value is 616.74.Ultimate analysis: calculated value is C:95.42%; H:4.58%; Test value is C:95.40%; H:4.60%.
Embodiment 5: compound 005 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(50mmol with the fluorenyl replacement), indenyl boric acid 15.20g(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 95 ℃, 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 22.59g, productive rate is more than 94%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 480.60; Test value is 480.58.Ultimate analysis: calculated value is C:94.97%; H:5.03%; Test value is C:94.95%; H:5.05%.
Embodiment 6: compound 006 synthetic
Concrete synthetic route is as follows:
Benzanthracenes bromo-derivative 22.27g(50mmol with the fluorenyl replacement), fluorenyl boric acid 21.00g(100mmol), sodium carbonate 21.20g(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 24.94g, productive rate is more than 94%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 530.66; Test value is 530.68.Ultimate analysis: calculated value is C:95.06%; H:4.94%; Test value is C:95.04%; H:4.96%.
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 3600cd/m
2, observing efficient under 10v voltage is 27Lm/w, chromaticity coordinates (CIE) value is x:0.16; Y:0.15 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. electroluminescent organic material that contains the Benzanthracenes derivative is characterized in that general structure is as follows:
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. a kind of electroluminescent organic material that contains the Benzanthracenes derivative according to claim 1 is characterized in that comprising the compound of following structural:
3. the preparation method who contains the electroluminescent organic material of Benzanthracenes derivative according to claim 1 and 2 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;
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, 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 who contains the electroluminescent organic material of Benzanthracenes derivative according to claim 3, 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 (7)
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| CN104513192A (en) * | 2013-09-30 | 2015-04-15 | 北京鼎材科技有限公司 | Benzoanthra[9,1-bc]carbazole derivative and applications thereof |
| JP2015124206A (en) * | 2013-12-27 | 2015-07-06 | 株式会社半導体エネルギー研究所 | Organic compound, light emitting element, display module, illumination module, light emitting device, display device, electronic device and illumination device |
| CN106188053A (en) * | 2016-07-07 | 2016-12-07 | 中节能万润股份有限公司 | A kind of electron transport material, preparation method and applications |
| CN106478358A (en) * | 2016-09-14 | 2017-03-08 | 中节能万润股份有限公司 | A kind of organic photoelectrical material containing spirane structure and its application |
| EP3533793A1 (en) * | 2018-02-28 | 2019-09-04 | Novaled GmbH | Organic electronic device, display and lighting devices comprising the same |
| CN112447915A (en) * | 2019-09-02 | 2021-03-05 | 冠能光电材料(深圳)有限责任公司 | High-performance organic electron transport material and OLED device application |
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| CN104513192A (en) * | 2013-09-30 | 2015-04-15 | 北京鼎材科技有限公司 | Benzoanthra[9,1-bc]carbazole derivative and applications thereof |
| CN104513192B (en) * | 2013-09-30 | 2019-03-26 | 北京鼎材科技有限公司 | A kind of benzo anthra [9,1-bc] carbazole derivates and its application |
| JP2015124206A (en) * | 2013-12-27 | 2015-07-06 | 株式会社半導体エネルギー研究所 | Organic compound, light emitting element, display module, illumination module, light emitting device, display device, electronic device and illumination device |
| CN106188053A (en) * | 2016-07-07 | 2016-12-07 | 中节能万润股份有限公司 | A kind of electron transport material, preparation method and applications |
| CN106188053B (en) * | 2016-07-07 | 2017-11-07 | 中节能万润股份有限公司 | A kind of electron transport material, preparation method and applications |
| CN106478358A (en) * | 2016-09-14 | 2017-03-08 | 中节能万润股份有限公司 | A kind of organic photoelectrical material containing spirane structure and its application |
| CN106478358B (en) * | 2016-09-14 | 2018-08-28 | 中节能万润股份有限公司 | A kind of organic photoelectrical material containing spirane structure and its application |
| 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 |
| CN112447914A (en) * | 2019-08-30 | 2021-03-05 | 冠能光电材料(深圳)有限责任公司 | High-performance organic semiconductor main body material and OLED device application |
| CN112447915A (en) * | 2019-09-02 | 2021-03-05 | 冠能光电材料(深圳)有限责任公司 | High-performance organic electron transport material and OLED device application |
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