CN103288812B - Containing thiophene electroluminescent organic material and its preparation method and application - Google Patents
Containing thiophene electroluminescent organic material and its preparation method and application Download PDFInfo
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- CN103288812B CN103288812B CN201210047363.1A CN201210047363A CN103288812B CN 103288812 B CN103288812 B CN 103288812B CN 201210047363 A CN201210047363 A CN 201210047363A CN 103288812 B CN103288812 B CN 103288812B
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- organic material
- thiophene
- electroluminescent organic
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- electroluminescent
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- 0 *c(cc1)cc2c1[n](-c1ccc(-c3cccc(-c4ccc(-[n]5c(ccc(*)c6)c6c6c5ccc(*)c6)[s]4)n3)[s]1)c1ccc(*)cc21 Chemical compound *c(cc1)cc2c1[n](-c1ccc(-c3cccc(-c4ccc(-[n]5c(ccc(*)c6)c6c6c5ccc(*)c6)[s]4)n3)[s]1)c1ccc(*)cc21 0.000 description 2
- VCQRVWGXBJQSAT-UHFFFAOYSA-N CCCCCCc(cc1)cc2c1[n](-c1ccc(-c3nc(-c4ccc(-[n]5c(ccc(CCCCCC)c6)c6c6cc(CCCCCC)ccc56)[s]4)ccc3)[s]1)c1ccccc21 Chemical compound CCCCCCc(cc1)cc2c1[n](-c1ccc(-c3nc(-c4ccc(-[n]5c(ccc(CCCCCC)c6)c6c6cc(CCCCCC)ccc56)[s]4)ccc3)[s]1)c1ccccc21 VCQRVWGXBJQSAT-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to field of organic electroluminescent materials, it discloses a kind of containing thiophene electroluminescent organic material and its preparation method and application; Following general formula should be had containing thiophene electroluminescent organic material:
in formula, R is hydrogen atom or C
1-C
6alkyl.Provided by the invention containing thiophene electroluminescent organic material, there is excellent thermostability, there is good solubility and film-forming properties, and by spectrum test, find that the maximum emission wavelength of this material is at blue light range; This electroluminescent organic material is due to the existence of pyridine ring, thiphene ring and carbazole in structure simultaneously, makes material have extraordinary carrier transmission performance.
Description
Technical field
The present invention relates to electroluminescent organic material, particularly relate to a kind of containing thiophene electroluminescent organic material and its preparation method and application.
Background technology
Along with the development of information age, there is the concern that the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating are more and more subject to people.OLED technology is paid close attention to by the scientist in the whole world, and relevant enterprise and laboratory are all in the research and development carrying out this technology.As a kind of novel LED technology, there is active illuminating, light, thin, good contrast, energy consumption are low, organic electroluminescence device that is that can be made into the features such as flexible device proposes higher requirement to material.
1987, Tang and VanSlyke of EastmanKodak company of the U.S. reported the breakthrough in organic electroluminescent research.And the application purpose such as total colouring and illumination will be realized, luminescent device must have certain efficiency and life-span.Blue light electroluminescence efficient, stable at present, white light parts are fewer, and the blue light material of high mobility, high thermal stability also compares shortage.
Thiophene is five member ring heterocyclic compound, and ring has 6 п electronics, meets Huckel's rule, have aromaticity, environmental stability is good.The cloud density of thiophene is high simultaneously, and therefore thiophene has unique optics, electrical properties, and its large electron density makes its HOMO orbital energy level reduce, and is conducive to hole transport, can produces indigo plant-green glow.
Summary of the invention
One of problem to be solved by this invention be to provide a kind of electronic transmission performance of having had and high thermal stability containing thiophene electroluminescent organic material.
A kind of containing thiophene electroluminescent organic material, there is following chemical structure of general formula:
In formula, R is hydrogen atom or C
1-C
6alkyl; Preferred R is the tertiary butyl.
Two of problem to be solved by this invention is the preparation method providing above-mentioned electroluminescent organic material, and step is as follows:
In atmosphere of inert gases, (be selected from the inert atmosphere that nitrogen or argon gas etc. are formed), by structural formula be
compound I and structural formula be
compound II per be dissolved in the organic solvent containing catalyzer and alkali lye with mol ratio 1: 2 ~ 1: 3, at 100 ~ 180 DEG C, carry out linked reaction 8 ~ 48h, obtained structural formula is
containing thiophene electroluminescent organic material (DRCzTPy); Wherein,
be 3,5-bis-(5-halogen-2-base) pyridine, X is Br or I;
for carbazole (R is hydrogen atom) or 3,6-dialkyl group carbazole, (R is C
1-C
6alkyl); Wherein, R is hydrogen atom or C
1-C
6alkyl, preferred R is the tertiary butyl; Reaction formula is as follows:
In above-mentioned preparation method, described catalyzer is selected from Cu, CuI, Pd (dba)
2with Pt-Bu
3(wherein, Pd (dba)
2with Pt-Bu
3mol ratio be 1: 3) mixture or Pd (OAc)
2with (t-Bu)
3pHBF
4(wherein, Pd (OAc)
2with (t-Bu)
3pHBF
4mol ratio be 1: 3) at least one in mixture, and the mole dosage of described metal catalyst is 0.005 ~ 0.5 times of starting compound II mole dosage; And
Alkali lye is selected from KOH, K
2cO
3or at least one in t-BuONa solution; And in described alkali lye, the mole dosage of alkali is 1 ~ 3 times of starting compound II mole dosage.
In above-mentioned preparation method, described organic solvent is at toluene, dimethylbenzene or chlorobenzene.
Three of problem to be solved by this invention is above-mentioned containing the application of thiophene electroluminescent organic material in organic electroluminescence device, is mainly used for emitting layer material.
Provided by the invention containing thiophene electroluminescent organic material, by differential thermal analysis, scan and characterize the performance of this kind containing thiophene electroluminescent organic material, result shows that this material has excellent thermostability.
Containing in thiophene electroluminescent organic material, thiophene is five member ring heterocyclic compound, and ring has 6 п electronics, meets Huckel's rule, have aromaticity, environmental stability is good; The cloud density of thiophene is high simultaneously, and therefore thiophene has unique optics, electrical properties, and its large electron density makes its HOMO orbital energy level reduce, and is conducive to hole transport, can produces indigo plant-green glow.
In addition, also carbazole group is contained containing in thiophene electroluminescent organic material, carbazole is electron rich group, the transmission performance of material can be improved, simultaneously due to its plane rigid structure, also contribute to the raising of material thermostability, and pyridine is electron deficiency group, the electronic transmission performance of material can be improved;
Such material has good solubility and film-forming properties, and by spectrum test, finds that the maximum emission wavelength of this material is at blue light range.
Preparation method containing thiophene electroluminescent organic material provided by the invention, technique is simple, is easy to control.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectra figure containing thiophene electroluminescent organic material (DCzTPy) film executing example 1 preparation.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Present embodiment discloses structural formula following containing thiophene electroluminescent organic material, i.e. 2,6-two (5-(9-carbazole) thiophene-2-base) pyridines (DCzTPy), wherein, R is hydrogen atom:
The preparation of two (5-(9-carbazole) thiophene-2-base) pyridine (DCzTPy) of 2,6-:
Add 3,5-bis-(the iodo-2-yl of 5-) pyridine 3mmol, carbazole 6.2mmol, toluene 25mL under nitrogen protection successively, under stirring, add Pd (OAc)
20.12mmol, t-BuONa7.2mmol, (t-Bu)
3pHBF
40.36mmol, return stirring linked reaction 18h at 110 DEG C.After reaction terminates, cooling, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain two (5-(9-carbazole) thiophene-2-base) the pyridine solid product of 2,6-.Productive rate: 49%.MALDI-TOF-MS：m/z574(M
+)。
Fig. 1 is the fluorescence emission spectra figure containing thiophene electroluminescent organic material (DCzTPy) film executing example 1 preparation; Its maximum emission wavelength, at 458nm place, belongs to blue light range.
Embodiment 2
Present embodiment discloses structural formula following containing thiophene electroluminescent organic material, i.e. 2,6-two (5-(3,6-Dimethylcarbazole-9-base) thiophene-2-base) pyridines (DMCzTPy), wherein, R is methyl:
The preparation of two (5-(3, the 6-Dimethylcarbazole-9-base) thiophene-2-base) pyridine (DMCzTPy) of 2,6-:
3,5-bis-(the bromo-2-yl of 5-) pyridine 3.0mmol is added successively, 3 under nitrogen protection; 6-Dimethylcarbazole 6.0mmol; dimethylbenzene 25mL, adds CuI0.03mmol, phenanthroline 0.09mmol, KOH18.0mmol under stirring, return stirring linked reaction 24h at 125 ~ 130 DEG C.After reaction terminates, cooling, poured into by reaction solution in dilute hydrochloric acid solution, toluene extracts, and organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain 2, two (5-(3,6-Dimethylcarbazole-9-base) thiophene-2-base) the pyridine solid product of 6-.Productive rate: 53%.MALDI-TOF-MS：m/z630(M
+)。
Embodiment 3
Present embodiment discloses structural formula following containing thiophene electroluminescent organic material, i.e. 2,6-two (5-(3,6-di-t-butyl carbazole-9-base) thiophene-2-base) pyridines (DtBuCzTPy), wherein, R is the tertiary butyl:
The preparation of two (5-(3, the 6-di-t-butyl carbazole-9-base) thiophene-2-base) pyridine (DtBuCzTPy) of 2,6-:
Add 3,5-bis-(the iodo-2-yl of 5-) pyridine 3.0mmol, 3,6-di-t-butyl carbazole 9.0mmol under argon shield successively, chlorobenzene 25mL, add Cu powder 4.5mmol, 18-under stirring and be preced with-61.0mmol, K
2cO
327.0mmol, 15mL chlorobenzene, return stirring linked reaction 48h at 180 DEG C.After reaction terminates, by a short silicagel column heat filtering, revolve after steaming removing chlorobenzene solvent and obtain crude product, again through silica gel column chromatography separating-purifying, finally obtain two (5-(3,6-di-t-butyl carbazole-9-base) thiophene-2-base) the pyridine solid product of 2,6-.Productive rate: 42%.MALDI-TOF-MS：m/z799(M
+)。
Embodiment 4
Present embodiment discloses structural formula following containing thiophene electroluminescent organic material, i.e. 2,6-two (5-(3,6-dihexyl carbazole-9-base) thiophene-2-base) pyridines (DHCzTPy), wherein, R is hexyl:
The preparation of two (5-(3, the 6-dihexyl carbazole-9-base) thiophene-2-base) pyridine (DHCzTPy) of 2,6-:
Add 3,5-bis-(the iodo-2-yl of 5-) pyridine 3.0mmol, 3,6-dihexyl carbazole 6.5mmol under argon shield successively, toluene 25mL, adds Pd (dba) under stirring
20.12mmol, t-BuOK7.2mmol, Pt-Bu
30.36mmol, return stirring linked reaction 48h at 110 DEG C.After reaction terminates, by a short silicagel column heat filtering, revolve after steaming removing chlorobenzene solvent and obtain crude product, again through silica gel column chromatography separating-purifying, finally obtain two (5-(3,6-dihexyl carbazole-9-base) thiophene-2-base) the pyridine solid product of 2,6-.Productive rate: 49%.MALDI-TOF-MS：m/z910(M
+)。
The contain thiophene organic semiconductor material obtained to above-described embodiment 1 to 4 has carried out thermogravimetric analyzer (TGA) detection, and result as shown in Table 1.
Table one is detected by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, when sweep velocity is 10 DEG C/min, the heat decomposition temperature of electroluminescent organic material in the embodiment obtained, its heat decomposition temperature more than (5% thermal weight loss), illustrates that this type of material has quite high thermostability up to 390 DEG C.
The heat decomposition temperature of table one electroluminescent organic material
| Compound | DCzTPy | DMCzTPy | DtBuCzTPy | DHCzTPy |
| Heat decomposition temperature (5% thermal weight loss)/DEG C | 390 | 398 | 407 | 402 |
The contain phenanthroline organic semiconductor material obtained to above-described embodiment 1 to 3 has carried out electronic mobility detection, and result as shown in Table 2.
Table two is electronic mobilities of electroluminescent organic material in the above-described embodiment recorded by field-effect transistor method, and its value is 5.5 × 10
-5cm
2(Vs)
-1, illustrate that this type of material has extraordinary carrier transmission performance.
The field-effect electronic mobility of table two electroluminescent organic material
| Compound | DCzTPy | DMCzTPy | DtBuCzTPy |
| Hole mobility/cm 2(Vs) -1 | 2.7×10 -4 | 1.0×10 -4 | 8.5×10 -5 |
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (7)
1. containing a thiophene electroluminescent organic material, it is characterized in that should having following general formula containing thiophene electroluminescent organic material:
In formula, R is hydrogen atom or C
1-C
6alkyl.
2. according to claim 1 containing thiophene electroluminescent organic material, it is characterized in that, R is the tertiary butyl.
3., containing a preparation method for thiophene electroluminescent organic material, it is characterized in that, this preparation method comprises the steps:
In atmosphere of inert gases, by structural formula be
chemical compounds I and structural formula be
compound ii, be dissolved in the organic solvent containing catalyzer and alkali lye with mol ratio 1:2 ~ 1:3, at 100 ~ 180 DEG C, carry out linked reaction 8 ~ 48h, obtaining structural formula is
containing thiophene electroluminescent organic material;
Wherein, X is Br or I; R is hydrogen atom or C
1-C
6alkyl;
Described catalyzer is selected from Cu, CuI, Pd (dba)
2with Pt-Bu
3mixture or Pd (OAc)
2with (t-Bu)
3pHBF
4at least one in mixture, the mole dosage of described metal catalyst is 0.005 ~ 0.5 times of compound ii mole dosage;
In described alkali lye, the mole dosage of alkali is 1 ~ 3 times of starting compound II mole dosage.
4. the preparation method containing thiophene electroluminescent organic material according to claim 3, it is characterized in that, R is the tertiary butyl.
5. the preparation method containing thiophene electroluminescent organic material according to claim 3, it is characterized in that, this alkali lye is selected from KOH, K
2cO
3or at least one in t-BuONa solution.
6. the preparation method containing thiophene electroluminescent organic material according to claim 3, it is characterized in that, described organic solvent is toluene, dimethylbenzene or chlorobenzene.
7. described in claim 1 or 2 containing the application of thiophene electroluminescent organic material in electroluminescent device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020115870A1 (en) * | 2000-11-21 | 2002-08-22 | Lin Jiann T?Apos;Suen | Heterarylbenzene compounds |
| WO2004058740A1 (en) * | 2002-11-29 | 2004-07-15 | Infineon Technologies Ag | Amino-substituted oligothiophenes as organic semiconductor materials |
-
2012
- 2012-02-27 CN CN201210047363.1A patent/CN103288812B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020115870A1 (en) * | 2000-11-21 | 2002-08-22 | Lin Jiann T?Apos;Suen | Heterarylbenzene compounds |
| WO2004058740A1 (en) * | 2002-11-29 | 2004-07-15 | Infineon Technologies Ag | Amino-substituted oligothiophenes as organic semiconductor materials |
Non-Patent Citations (1)
| Title |
|---|
| Electro-Functional Octupolar π-Conjugated Columnar Liquid Crystals;Takuma Yasuda，等;《J. Am. Chem. Soc.》;20110726;第133卷;第13437-13444页 * |
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