CN103525400A - Styryl derivative organic electroluminescent material and preparation method thereof - Google Patents
Styryl derivative organic electroluminescent material and preparation method thereof Download PDFInfo
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- CN103525400A CN103525400A CN201310422629.0A CN201310422629A CN103525400A CN 103525400 A CN103525400 A CN 103525400A CN 201310422629 A CN201310422629 A CN 201310422629A CN 103525400 A CN103525400 A CN 103525400A
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Abstract
The invention discloses a styryl derivative organic electroluminescent material. The structural general formula of the material is shown in the specification, wherein R1 group is a C6-C12 aromatic group, and R2 group is a C8-C18 aromatic heterocyclic group or a C9-C15 polycyclic aromatic group. The styryl derivative has a symmetric chemical structure and forms conjugation to a certain extent in molecular design; all carbazole group, fluorene and anthracene are excellent auxochrome groups to realize improvement on the performance; a blue-light device prepared by using the material can meet the requirements of industrial production. Since the material has higher luminous efficiency, the material can be applied to electroluminescent devices as an organic light-emitting material, a light-emitting main material or a transporting material; as shown by the data results of application embodiments, the performance is obviously improved and the organic electroluminescent material is a very promising material compared with contrast materials.
Description
Technical field
The invention belongs to organic photoelectrical material field, be specifically related to a kind of styryl derivative class luminous organic material and preparation method thereof.
Background technology
Distyryl derivative is considered to the good blue emitting material of a class, and molecule is nonplanar structure because of space steric effect, and glow color is relevant with their substituting group, and electroluminescent peak is many between 440-490nm.In order to improve purity of color and the luminous efficiency of luminescent device, conventionally in main body luminescent material, add a small amount of dopant material, the wavelength of main body changes according to the wavelength of dopant material, therefore according to the kind of dopant material, can obtain the light with required wavelength.This research attempts carbazole ring to introduce in distyryl, hope, by the introducing of carbazole group, improves the thermostability of material, improves stability and the life-span of device, the introducing of carbazole group also likely changes rigidity, the steric hindrance of material, improves its solvability, film-forming properties etc.
US Patent No. 20080001123 discloses a series of styrenic derivatives that can be used as blue light dopant material, comprising 4, and 4 '-bis-[4-(two tolyl amino) styryl] biphenyl.Its structural formula is as follows:
But this patent does not have the synthetic method of this compounds carries out careful research report, to it, should not be used as further discussion yet.
Summary of the invention
The present invention cannot meet the problem of suitability for industrialized production in order to solve existing blue light material, and a kind of higher photoluminescence efficiency that has is provided, and cost is low, a kind of styryl derivative class luminous organic material that productive rate and purity are high and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of styryl derivative class luminous organic material, the general structure of this material is as follows:
Wherein, R
1group is C
6-C
12aromatic group, R
2group is C
8-C
18aromatic heterocyclic radical, C
9-C
15fused ring aryl.
Preferred R
1group is phenyl or xenyl; Preferred R
2group is N-phenyl-3-carbazyl, 4-(9,10-bis-(2-naphthyl) anthryl benzene.
Preferred styryl derivative class luminous organic material of the present invention is:
R
1for phenyl, R
2for N-phenyl-3-carbazyl;
R
1for xenyl, R
2for N-phenyl-3-carbazyl;
R
1for phenyl, R
2for (4-(9,10-bis-(2-naphthyl) anthryl) benzene;
R
1for xenyl, R
2for (4-(9,10-bis-(2-naphthyl) anthryl) benzene.
Styryl derivative class luminous organic material, it is any one in following 001-004 chemical structural formula:
Be exactly concrete structure formation more above, but this series compound is not limited to these listed chemical structures.Every take structural formula (1) as basis, R
1, R
2the compound that group is respectively the simple transformation of group in all scopes of definition all should be included.
The preparation method of described vinylbenzene base class luminous organic material is also provided in the present invention, and this preparation method's concrete steps and condition are as follows:
For 1:2 ~ 3.5, take containing R in molar ratio
1substituent 4,4 '-dibenzyl diethyl phosphoric acid and R
2substituent aldehyde compound; Add potassium tert.-butoxide, potassium tert.-butoxide with containing R
1substituent 4,4 '-dibenzyl diethyl phosphoric acid 1:2 ~ 2.5; Temperature of reaction is 25 ℃ ~ 30 ℃, and the reaction times is 10 ~ 20 hours; After completion of the reaction, reaction solution is cooled to room temperature, and recrystallization is standing, filters, and the filter cake obtaining, uses toluene recrystallization, obtains described styryl analog derivative.
The invention has the beneficial effects as follows:
1, styryl analog derivative provided by the invention, in molecular designing, chemical structure is symmetrical, form conjugation to a certain degree, carbazole group, fluorenes, anthracene are all good auxochrome groups, realize the improvement to performance, and the blue-light device being made into material of the present invention can meet the demand of suitability for industrialized production.
Particularly, when R is N-phenyl carbazole base, the luminous efficiency of such luminous organic material preparing in dilute solution can reach 97%, and the luminous efficiency in film can reach 61%.
2, styryl analog derivative of the present invention is owing to having higher luminous efficiency, can be used as luminous organic material, luminous material of main part or transport material, be applied on electroluminescent device, data results by Application Example shows, comparing and be significantly improved with contrast material, is a very promising class electroluminescent organic material.
Embodiment
The synthetic route of embodiment 1 compound 001 is as follows:
At normal temperatures by 3.78g (10mmol) 4, 4 '-dibenzyl diethyl phosphoric acid benzene, 5.47g (20mmol) 4-(8H-carbazole-9(9H)-yl) phenyl aldehyde, 2.24g (20mmol) potassium tert.-butoxide and 50mL tetrahydrofuran solution, after stirring and dissolving, join in 250mL reaction flask, setting temperature of reaction is 25 ℃, reaction times is 12 hours, after reaction finishes, reaction solution is cooled to room temperature, reaction product is poured in 100mL ethanol and stirred, the standing yellow-green colour solid of separating out, filter, the filter cake obtaining is with obtaining glassy yellow pressed powder after toluene recrystallization, after dry, obtain 5.35g, yield is 87%, purity is 99.0%.Ultimate analysis: mass spectrum: calculated value is 614.78; Test value is 614.76.Ultimate analysis: calculated value is C:89.87%; H:5.57%; N:4.56%; Test value is C:89.86%; H:5.56%; N:4.58%.
The synthetic route of embodiment 2 compounds 002 is as follows:
At normal temperatures by 4.54g (10mmol) 4, 4 '-dibenzyl diethyl phosphoric acid biphenyl, 6.83g (25mmol) 4-(8H-carbazole-9(9H)-yl) phenyl aldehyde, 2.47g (22mmol) potassium tert.-butoxide and 50mL tetrahydrofuran solution, after stirring and dissolving, join in 250mL reaction flask, setting temperature of reaction is 26 ℃, reaction times is 14 hours, after reaction finishes, reaction solution is cooled to room temperature, reaction product is poured in 100mL ethanol and stirred, the standing yellow-green colour solid of separating out, filter, the filter cake obtaining is with obtaining glassy yellow pressed powder after toluene recrystallization, after dry, obtain 6.15g, yield is 89%, purity is 99.0%.Ultimate analysis: mass spectrum: calculated value is 690.87; Test value is 690.85.Ultimate analysis: calculated value is C:90.40%; H:5.54%; N:4.05%; Test value is C:90.41%; H:5.56%; N:4.02%.
The synthetic route of embodiment 3 compounds 003 is as follows:
At normal temperatures by 3.78g (10mmol) 4, 4 '-dibenzyl diethyl phosphoric acid benzene, 16.04g (30 mmol) 4-(9, 10-bis-(naphthalene-2-yl) anthracene-2-yl) phenyl aldehyde, 2.69g (24mmol) potassium tert.-butoxide and 50mL tetrahydrofuran solution, after stirring and dissolving, join in 250mL reaction flask, setting temperature of reaction is 27 ℃, reaction times is 16 hours, after reaction finishes, reaction solution is cooled to room temperature, reaction product is poured in 100mL ethanol and stirred, the standing yellow-green colour solid of separating out, filter, the filter cake obtaining is with obtaining glassy yellow pressed powder after toluene recrystallization, after dry, obtain 9.80g, yield is 86%, purity is 99.0%.Ultimate analysis: mass spectrum: calculated value is 1139.42; Test value is 1139.43.Ultimate analysis: calculated value is C:94.87%; H:5.13%; Test value is C:94.88%; H:5.12%.
The synthetic route of embodiment 4 compounds 004 is as follows:
At normal temperatures by 4.54g (10mmol) 4, 4 '-dibenzyl diethyl phosphoric acid biphenyl, 18.71g (35mmol) 4-(9, 10-bis-(naphthalene-2-yl) anthracene-2-yl) phenyl aldehyde, 2.81g (25mmol) potassium tert.-butoxide and 50mL tetrahydrofuran solution, after stirring and dissolving, join in 250mL reaction flask, setting temperature of reaction is 28 ℃, reaction times is 18 hours, after reaction finishes, reaction solution is cooled to room temperature, reaction product is poured in 100mL ethanol and stirred, the standing yellow-green colour solid of separating out, filter, the filter cake obtaining is with obtaining glassy yellow pressed powder after toluene recrystallization, after dry, obtain 5.35g, yield is 84%, purity is 99.0%.Ultimate analysis: mass spectrum: calculated value is 1215.52; Test value is 1215.54.Ultimate analysis: calculated value is C:94.86%; H:5.14%; Test value is C:94.85%; H:5.15%.
Application implementation case
We become sample preparation respectively concentration is 1 * 10
-6the solution of mol/L, is used Edinburdh-FLS920 equipment, and spin-coating method is made into film, has tested respectively their luminous efficiency, and concrete data are as following table.
The luminous efficiency of gained compound in table 1 embodiment
| Compound | Luminous efficiency in dilute solution | Luminous efficiency in film |
| 101 | 95% | 53% |
| 102 | 97% | 61% |
| 103 | 96% | 58% |
| 104 | 92% | 51% |
From the data of table 1, can find out, four kinds of new synthetic compounds luminous efficiency in luminous efficiency and film in dilute solution is higher, according to application example, we are applied to material in organic electroluminescence device, by data test and comparison, we find the good luminous material of main part of electroluminescent organic material, particularly Performance Ratio and transport material that this class material is excellent property really, are very promising class electroluminescent organic materials.
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 convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (3)
1. a styryl derivative class electroluminescent organic material, is characterized in that: the general structure of this material as the formula (1):
Formula (1);
Wherein, R
1group is C
6-C
12aromatic group, R
2group is C
8-C
18aromatic heterocyclic radical, C
9-C
15fused ring aryl.
2. a kind of styryl derivative class electroluminescent organic material according to claim 1, is characterized in that: R
1group is phenyl or xenyl; R
2group is N-phenyl-3-carbazyl, 4-(9,10-bis-(2-naphthyl) anthryl benzene.
3. the preparation method of a kind of styryl derivative class electroluminescent organic material according to claim 1 and 2, is characterized in that: for 1:2 ~ 3.5, take containing R in molar ratio
1substituent 4,4 '-dibenzyl diethyl phosphoric acid and R
2substituent aldehyde compound; Add potassium tert.-butoxide, potassium tert.-butoxide with containing R
1substituent 4,4 '-dibenzyl diethyl phosphoric acid 1:2 ~ 2.5; Temperature of reaction is 25 ℃ ~ 30 ℃, and the reaction times is 10 ~ 20 hours; After completion of the reaction, reaction solution is cooled to room temperature, and recrystallization is standing, filters, and the filter cake obtaining, uses toluene recrystallization, obtains described styryl analog derivative.
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| US20090212747A1 (en) * | 2006-04-03 | 2009-08-27 | James Becker | Power control system and method |
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| CN102224148A (en) * | 2008-09-23 | 2011-10-19 | 株式会社Lg化学 | Novel compound, method for preparing same and organic electronic device using same |
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| JP2010212112A (en) * | 2009-03-11 | 2010-09-24 | Kyushu Univ | Method of controlling molecular orientation direction of charge-transporting amorphous thin film, and method of manufacturing charge-transporting amorphous thin film |
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Application publication date: 20140122 |