CN102911656A - Derivative-conjugated organic light-emitting material and preparation method thereof - Google Patents
Derivative-conjugated organic light-emitting material and preparation method thereof Download PDFInfo
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- CN102911656A CN102911656A CN2012104158886A CN201210415888A CN102911656A CN 102911656 A CN102911656 A CN 102911656A CN 2012104158886 A CN2012104158886 A CN 2012104158886A CN 201210415888 A CN201210415888 A CN 201210415888A CN 102911656 A CN102911656 A CN 102911656A
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Abstract
The invention provides a derivative-conjugated organic light-emitting material and a preparation method of the derivative-conjugated organic light-emitting material, relating to organic optoelectronic materials and preparation methods of the organic optoelectronic materials. The structural general formula of the derivative-conjugated organic light-emitting material is shown in the specification, wherein the group A represents an aromatic group. The preparation method of the derivative-conjugated organic light-emitting material comprises the following steps: adding aryl halide A-Br, arylboronic acid, alkali and a solvent to degas a reaction system; and finally adding a catalyst to end the reaction. The derivative-conjugated organic light-emitting material can form a large high-pi conjugated system, has good film-forming property, is suitable to be used as an OLED (Organic Light Emitting Diode) device and meets the requirements on light-emitting materials.
Description
Technical field
The present invention relates to chemical technology field, relate to organic photoelectrical material and preparation method.
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 be the study hotspot of present organic electroluminescent industry to the preparation of original material 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 relatively 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, so that OLED makes 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 affair.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of efficient derivative conjugated body luminous organic material.
The present invention also discloses the preparation method of this luminous organic material simultaneously.
Technical scheme of the present invention is as follows:
The present invention's exploitation provides the novel large pi-conjugated aromatic hydrocarbon luminous organic material that contains, and contains benzopyran structure, has provided simultaneously corresponding synthetic method and the application in organic electroluminescence device.The general structure of this luminous organic material is as follows:
The A group represents aromatic group in the formula, and concrete structure is as follows:
Wherein * is the site that links to each other with phenyl ring.
Shown in the electroluminescent organic material that structural formula of the present invention represents specific as follows, but be not limited to these given compounds of following instance:
These chemical structures of row.Every take above-mentioned general structure as the basis, the arbitrary structures of the concrete structure that provides before the A group is respectively is in 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 in.
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.The synthetic route of its structural formula is as follows:
Step is:
Add and contain aryl halide A-Br, aryl boric acid, alkali and solvent, degassed to reaction system, add catalyzer, be warming up to 70-100 ℃, reacted 24-30 hour;
In the described step, aryl halide A-Br and aryl boric acid mol ratio are 2.5 ~ 2.9:1.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 4 ~ 8:1, the consumption of described solvent is 20 ~ 35 times of aryl halide weight, described catalyzer is preferably four, the triphenyl phosphorus palladium, and the mol ratio of catalyzer and aryl halide is 1:20 ~ 1000.Described alkali is preferably yellow soda ash, and the mol ratio of alkali and aryl halide is 1 ~ 4:1.
The synthetic aftertreatment of described structural formula compounds mainly comprises suction filtration, washing and oven dry.
Preferred steps of the present invention is;
Add and contain aryl halide A-Br, aryl boric acid, alkali and solvent, degassed to reaction system, add catalyzer, be warming up to 80-90 ℃, reacted 26-28 hour;
In the described step, aryl halide A-Br and aryl boric acid mol ratio are 2.7:1, described solvent is organic solvent and water, described organic solvent is selected tetrahydrofuran (THF), and the volume ratio of organic solvent and water is 6:1, and the consumption of described solvent is 25 times of aryl halide weight, described catalyzer is four, the triphenyl phosphorus palladium, the mol ratio of catalyzer and aryl halide is 1:500, and described alkali is preferably yellow soda ash, and the mol ratio of alkali and aryl halide is 3:1.
Product derivative conjugated system of the present invention is large, can form larger large pi-conjugated system, film forming properties is good, be suitable as the OLED device, particularly by replacing the introducing of F atom, transition of electron can be regulated, the transmitting boundary of blue light differing materials from light blue to dark blue can be formed, satisfy the demand to luminescent material, particularly present needed light blue luminescent material.This class material synthetic and purify fairly simplely simultaneously, material is purified easily, and is with low cost, can satisfy the industrialization development demand.Can realize the adjusting of the usefulness aspect of material, and can implementation efficiency significantly improve, at film forming properties, the aspect in life-span all is significantly improved, and synthetic easy, of many uses, can as in the multiple material of device, have a extensive future.
Embodiment
Case study on implementation:
Synthesizing of embodiment 1 compound B-11 01
Under nitrogen protection system, take by weighing 9-bromine-N-phenylcarbazole 35.31g, aryl boric acid 17.3g puts into reaction system, adds anhydrous Na
2CO
3Solid 23.32g adds entry 110ml in the system, the toluene 220ml of adding, and under nitrogen protection, catalyst P d(PPh
3)
45.77g, the lower 90 ℃ of isothermal reaction 8-12 of nitrogen protection hours, reacted cooling, suction filtration, washing, extraction, concentrated, methylene dichloride is made solvent, crosses silica gel and does column chromatography, and is concentrated, obtains off-white color the finished product 23.2g, and productive rate is that 85%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 543.20; Test value is 543.17.Ultimate analysis: calculated value C:92.79%; H:4.64%; N:2.58%; Test value is: C:92.76%; H:4.62%; N:2.55%.
Synthesizing of embodiment 2 compound B-11s 04
Under nitrogen protection system, take by weighing 2-bromine anthracene 30.40g, aryl boric acid 19.5g puts into reaction system, adds anhydrous Na
2CO
3Solid 20.6g adds entry 100ml in the system, the toluene 220ml of adding, and under nitrogen protection, catalyst P d(PPh
3)
45.77g, the lower 90 ℃ of isothermal reaction 8-12 of nitrogen protection hours, reacted cooling, suction filtration, washing, extraction, concentrated, methylene dichloride is made solvent, crosses silica gel and does column chromatography, and is concentrated, obtains off-white color the finished product 23.14g, and productive rate is that 89%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 478.17; Test value is 478.15.Ultimate analysis: calculated value C:95.37%; H:4.63%; Test value is: C:95.35%; H:4.60%.
Synthesizing of embodiment 3 compound B-11s 08
Under nitrogen protection system, take by weighing 6-phenanthryl 26. g, aryl boric acid 19.5g puts into reaction system, adds anhydrous Na
2CO
3Solid 21.2g adds entry 100ml in the system, the toluene 210ml of adding, and under nitrogen protection, catalyst P d(PPh
3)
45.77g, the lower 90 ℃ of isothermal reaction 8-12 of nitrogen protection hours, reacted cooling, suction filtration, washing, extraction, concentrated, methylene dichloride is made solvent, crosses silica gel and does column chromatography, and is concentrated, obtains off-white color the finished product 21.61g, and productive rate is more than 85%, and HPLC purity is greater than 98%.Mass spectrum: calculated value is 478.17; Test value is 478.15.Ultimate analysis: calculated value C:95.37%; H:4.63%; Test value is: C:95.35%; H:4.60%.
The synthetic method of B series compound is identical with B101, and just the reaction raw materials halogenated aryl hydrocarbon is different, and it is corresponding different to obtain product, and the product result is as follows:
Compound B-11 02: similar to the synthetic method of B101, difference is to participate in reaction with 2-naphthyl 21.87g as initial feed, generates target product 20.85g.Productive rate is that 82%, HPLC purity is greater than 99%.Mass spectrum: calculated value is 428.16; Test value is 428.15.Ultimate analysis: calculated value C:95.30%; H:4.70%; Test value is: C:95.27%; H:4.68%.
Compound B-11 03: similar to the synthetic method of B101, difference is to participate in reaction with 2-bromine pyrene 28.73g as initial feed, generates target product 27.52g.Productive rate is that 84%, HPLC purity is greater than 99%.Mass spectrum: calculated value is 502.17; Test value is 502.15.Ultimate analysis: calculated value C:95.59%; H:4.41%; Test value is: C:95.56%; H:4.38%.
Compound B-11 05: similar to the synthetic method of B101, difference is to participate in reaction with non-that alkene of 5-bromine 27.00g as initial feed, generates target product 25.17g.Productive rate is that 83%, HPLC purity is greater than 99%.Mass spectrum: calculated value is 466.17; Test value is 466.15.Ultimate analysis: calculated value C:95.25%; H:4.75%; Test value is: C:95.23%; H:4.72%.
Compound B-11 06: similar to the synthetic method of B101, difference is to participate in reaction with 2-Xiu perylene 36.43g as initial feed, generates target product 33.81g.Productive rate is that 84%, HPLC purity is greater than 99%.Mass spectrum: calculated value is 552.19; Test value is 552.17.Ultimate analysis: calculated value C:95.62%; H:4.38%; Test value is: C:95.60%; H:4.36%.
Compound B-11 07: similar to the synthetic method of B101, difference is that 9-dimethyl fluorene 29.30g participates in reaction as initial feed with 3-bromo-9, generates target product 28.24g.Productive rate is that 85%, HPLC purity is greater than 99%.Mass spectrum: calculated value is 494.20; Test value is 494.17.Ultimate analysis: calculated value C:94.70%; H:5.30%; Test value is: C:94.68%; H:5.27%.
Application implementation case 1
The device architecture of case study on implementation 1 is identical with making method to be as luminescent material with the material that synthesizes implementation method B101.The device architecture of making is [ITO/NPB (20nm)/B101(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, the velocity of evaporation of Al is 2/s, and vacuum keep is the following vacuum tightness of 10-5pa normal atmosphere.
The test result of device is cut-in voltage 6v, and high-high brightness is 3800cd/m2, and observing efficient under the 10v voltage is 26lm/w, and chromaticity coordinates (CIE) value is x:0.18; Y:0.16 obtains a blue device, and life-span transformation period of device is 28000h.
Other materials is made device, and device architecture is identical, just makes material of main part with different materials, and test result is as follows:
The luminous efficiency of gained compound among table 1 embodiment
Can find out that from the data of table 1 novel electroluminescent organic material has high luminous efficiency among the embodiment, 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 the electroluminescent device.Simultaneously according to application example 1-4, we are applied to material in the organic electroluminescence device, by data test and comparison, we find electroluminescent organic material, particularly Performance Ratio that this class material is excellent property preferably luminous material of main part and transport material 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, for those of ordinary skills, can be improved according to the above description or conversion that all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (3)
1. a derivative conjugated body luminous organic material is characterized in that; General structure is as follows:
The A group represents aromatic group in the formula, structure specific as follows
Wherein * is the site that links to each other with phenyl ring.
2. the preparation method of derivative conjugated body luminous organic material according to claim 1, its feature may further comprise the steps to be finished:
Add and contain aryl halide A-Br, aryl boric acid, alkali and solvent, degassed to reaction system, add catalyzer, be warming up to 70-100 ℃, reacted 24-30 hour;
In the described step, aryl halide A-Br and aryl boric acid mol ratio are 2.5 ~ 2.9:1, and 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 4 ~ 8:1, the consumption of described solvent is 20 ~ 35 times of aryl halide weight, described catalyzer is preferably four, the triphenyl phosphorus palladium, the mol ratio of catalyzer and aryl halide is 1:20 ~ 1000, described alkali is preferably yellow soda ash, and the mol ratio of alkali and aryl halide is 1 ~ 4:1;
The synthetic aftertreatment of described structural formula compounds mainly comprises suction filtration, washing and oven dry.
3. the preparation method of derivative conjugated body luminous organic material according to claim 2, its feature may further comprise the steps to be finished:
Add and contain aryl halide A-Br, aryl boric acid, alkali and solvent, degassed to reaction system, add catalyzer, be warming up to 80-90 ℃, reacted 26-28 hour;
In the described step, aryl halide A-Br and aryl boric acid mol ratio are 2.7:1, described solvent is organic solvent and water, described organic solvent is selected tetrahydrofuran (THF), and the volume ratio of organic solvent and water is 6:1, and the consumption of described solvent is 25 times of aryl halide weight, described catalyzer is four, the triphenyl phosphorus palladium, the mol ratio of catalyzer and aryl halide is 1:500, and described alkali is preferably yellow soda ash, and the mol ratio of alkali and aryl halide is 3:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614133A (en) * | 2013-11-08 | 2014-03-05 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method thereof |
| WO2023127845A1 (en) * | 2021-12-27 | 2023-07-06 | 出光興産株式会社 | Compound, organic electroluminescent element, and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008270394A (en) * | 2007-04-18 | 2008-11-06 | Mitsui Chemicals Inc | Organic transistor |
| WO2011106990A1 (en) * | 2010-03-01 | 2011-09-09 | The Hong Kong University Of Science And Technology | Light emitting tetraphenylene derivatives, its method for preparation and light emitting device using the same derivatives |
-
2012
- 2012-10-26 CN CN2012104158886A patent/CN102911656A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008270394A (en) * | 2007-04-18 | 2008-11-06 | Mitsui Chemicals Inc | Organic transistor |
| WO2011106990A1 (en) * | 2010-03-01 | 2011-09-09 | The Hong Kong University Of Science And Technology | Light emitting tetraphenylene derivatives, its method for preparation and light emitting device using the same derivatives |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614133A (en) * | 2013-11-08 | 2014-03-05 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method thereof |
| WO2023127845A1 (en) * | 2021-12-27 | 2023-07-06 | 出光興産株式会社 | Compound, organic electroluminescent element, and electronic device |
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Application publication date: 20130206 |