CN103289676A - Red-light-emitting material and applications thereof - Google Patents
Red-light-emitting material and applications thereof Download PDFInfo
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- CN103289676A CN103289676A CN2013101419836A CN201310141983A CN103289676A CN 103289676 A CN103289676 A CN 103289676A CN 2013101419836 A CN2013101419836 A CN 2013101419836A CN 201310141983 A CN201310141983 A CN 201310141983A CN 103289676 A CN103289676 A CN 103289676A
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Abstract
The invention relates to a red-light-emitting material and applications thereof. The material is a star-type poly-substituted compound with triindene serving as a core and a thiophene-benzothiazole derivative serving as branches, and the compound has the general structure shown in formula (I), wherein X represents a thiophene derivative; and the thiophene derivative has the following structure: R represents a C1-C12 alkyl group, and a C1-C12 alkyloxy group, N represents a nitrogen atom, and S represents a sulfur atom. The material has characteristics of adjustable energy levels, narrow band gaps, high thermal stability, high glass-transition temperature, and easy formation of uniform amorphous films; and the material can be prepared for thin-film devices by a simple solution film-formation method, and has important potential applications in the field of organic photoelectron, especially in producing red-light-emitting organic electroluminescent devices.
Description
Technical field:
The invention belongs to photoelectric material and applied technical field, be specifically related to a kind of electroluminescent organic material, relate more specifically to a kind of star-type multi-arm structured material and preparation method thereof and application; This material be with three and indenes be nuclear, be the star-like polysubstitution compound of an arm with thiophene-benzene thiazole derivative, can be used as luminescent material and be widely used in organic luminescent device, particularly stability and high efficiency red organic electrofluorescence thin-film device.
Background technology:
(OrganicLight-EmittingDiodes OLED) in that the important application prospect is arranged aspect flat pannel display and the solid state lighting, has caused people's extensive concern to Organic Light Emitting Diode.The red, green, blue three primary colours are for realizing that panchromatic demonstration is most important.Green light material has reached the practicability requirement at present, and the development of ruddiness and blue light material relatively lags behind, and its luminous efficiency and fluorescence lifetime are lower.And to realize that the red light material of high-level efficiency, high fluorescence lifetime and device thereof remain the challenging problem in organic electroluminescent field.
The ruddiness electroluminescent organic material that uses is porphyrins, pyrans class dyestuff mostly at present, these materials have bigger dipole moment and long conjugated structure, the stronger De π of intermolecular existence – π interacts, and can aggravate molecular aggregates, causes fluorescent quenching.In the device preparation, red light material is doped in the material of main part more and uses to avoid cancellation, can influence life-span and the performance of device but mix.Integrating luminous and can be used for preparing non-doping type OLED with the subject type red light material electric charge transfer function, is the important research trend of present red light material.
For electroluminescent organic material, molecular designing is become hub-and-spoke configuration, not only increase the space steric effect of target material, interaction and accumulation between the stiff molecule chain that obtains are restricted, the crystallinity that suppresses material effectively, improve amorphous performance, reduce the cancellation effect of material when solid-state simultaneously, and can significantly strengthen the solid-state light emission performance of target material.On the basis of previous work, the present invention design synthesized a kind of with three and indenes be nuclear, thiophene-benzene thiazole derivative be the star-type multi-arm main structure body type red light material of arm.Wherein three and the indenes unit be rigid planar structure, it is good to have solvability, light, thermostability height are easy to advantages such as chemically modified; The benzene thiazole is typical n receptor unit; Thiophene and three also indenes is that common p-type is given electronic unit.The narrowband gap conjugated molecular material of the star-like many branching p-n junction of this class structure can prepare the organic electronic thin-film device by easy solution film forming mode, has considerable application prospect at aspects such as the organic film photoelectric device of realizing stability and high efficiency such as organic electroluminescence devices.
Summary of the invention:
Technical problem: the object of the present invention is to provide a kind of red organic electrofluorescence material and preparation method thereof and application, luminous intensity, luminous efficiency, purity of color that makes red light material etc. is increased dramatically.Can be used as active material and be applied to aspects such as organic luminescent device, organic solar batteries device and organic memory device, particularly be applied to prepare the ruddiness Organic Light-Emitting Display device of stability and high efficiency.
Technical scheme: the present invention proposes a kind of based on star-type multi-arm structural narrow band gap material, be with three and indenes be nuclear, be the polysubstitution compound of an arm with thiophene-benzene thiazole derivative that its formula is as shown in the formula shown in the I:
In the general formula I, X is thiophene derivant, its array structure specific as follows:
Wherein, R is C
1-C
12Alkyl; C
1-C
12Alkoxyl group; N is nitrogen-atoms, and S is sulphur atom.
The structure that can also have Formula Il based on star-type multi-arm structural narrow band gap material:
Among the general formula I I, X is thiophene derivant, its array structure specific as follows:
Wherein, R is C
1-C
12Alkyl; C
1-C
12Alkoxyl group; N is nitrogen-atoms, and S is sulphur atom.
Based on the application of star-type multi-arm structural narrow band gap material, this material is applied to organic electroluminescence device, and device architecture is anode/hole transmission layer/luminescent layer/electron transfer layer/negative electrode, and wherein star-type multi-arm structure thiophene benzene thiazole derivative is as luminescent layer.
Beneficial effect: the star-type multi-arm structure thiophene derivant red light material that the present invention proposes has following characteristics: the molecular structure that (1) is star-like, significantly increased the space steric effect of target material, interaction and accumulation between the stiff molecule chain that obtains are restricted, reduce the cancellation effect of material when solid-state simultaneously, significantly strengthened the solid-state light emission performance of target material; (2) introducing of benzene thiazole strengthens the luminous intensity of molecule; (3) the second-order transition temperature height, can form the unformed film of thermostability height, good uniformity; (4) can prepare thin-film device by easy solution film forming mode.Therefore, using this material can obtain spectrum and the stabilizing device performance of red emission, excellence efficiently as the organic electroluminescence device of luminescent layer, is a kind of ruddiness electroluminescent organic material with important application prospect.
Description of drawings
Fig. 1 is star-type multi-arm structured material Tr2RT's
1HNMR figure.
Fig. 2 is star-type multi-arm structured material Tr2RT's
13CNMR figure.
Fig. 3 is star-type multi-arm structured material Tr3RT's
1HNMR figure.
Fig. 4 is star-type multi-arm structured material Tr3RT's
13CNMR figure.
Fig. 5 is star-type multi-arm structured material Tr6RT's
1HNMR figure.
Fig. 6 is star-type multi-arm structured material Tr6RT's
13CNMR figure.
Fig. 7 is that the star-type multi-arm structured material is respectively at THF(10
-5M) UV under and PL curve.
Fig. 8 is ruddiness device A-C EL curve under voltage 9V.
Fig. 9 is ruddiness device A-C brightness-voltage-to-current densimetric curve.
Figure 10 is ruddiness device A-C current efficiency-current density curve.
Embodiment
A kind of star-type multi-arm structured material, be with three and indenes be nuclear, be the polysubstitution compound of an arm with thiophene-benzene thiazole derivative that its formula is as shown in the formula shown in the I:
In the general formula I, X is thiophene derivant, and it has following array structure:
Wherein, R is the alkyl of C1-C12, the alkoxyl group of C1-C12; N is nitrogen-atoms, and S is sulphur atom.
The structure that can also have Formula Il based on star-type multi-arm structural narrow band gap material:
Among the general formula I I, X is thiophene derivant, its array structure specific as follows:
Wherein, R is C
1-C
12Alkyl; C
1-C
12Alkoxyl group; N is nitrogen-atoms, and S is sulphur atom.
Below the present invention will be further described by some embodiment, but embodiment does not limit covering scope of the present invention:
Embodiment 1:
Reaction formula
According to reaction formula, compound 1 and duplex tetramethyl ethylene ketone boric acid ester, Potassium ethanoate is at Pd (dppf)
2Cl
2Do and the Suzuki linked reaction takes place under the condition of catalyzer make compound 2.With products therefrom 2 and 4-bromo-7-(5-hexyl thiophene-2-yl)-2,1, the 3-benzothiazole is at Pd (pph
3)
4Do and the Suzuki linked reaction takes place under the condition of catalyzer make target compound Tr2RT, productive rate 61%.
1HNMR(CDCl
3,400MHz):δ8.56-8.58(d,3H),8.15-8.17(d,6H),8.01-8.02(d,3H),7.95-7.97(d,3H),7.89-7.91(d,3H),3.05-3.12(m,6H),2.91-2.95(t,6H),2.24-2.31(m,6H),1.75-1.83(m,6H),1.35-1.48(m,18H),0.87-1.01(m,48H),0.61-0.71(m,27H).
13CNMR(CDCl
3,100MHz):δ154.17,154.12,153.01,147.93,146.02,140.51,138.17,136.94,135.32,132.39,127.98,127.54,126.58,125.30,125.25,124.76,122.95,56.00,37.13,31.94,31.66,31.60,30.36,29.71,29.63,29.37,28.88,24.15,22.70,22.62,22.37,14.14,13.96.
Embodiment 2:
According to reaction formula, compound 1 and duplex tetramethyl ethylene ketone boric acid ester, Potassium ethanoate is at Pd (dppf)
2Cl
2Do and the Suzuki linked reaction takes place under the condition of catalyzer make compound 2.With products therefrom and 4-bromo-7-(4-hexyl thiophene-2-yl)-2,1, the 3-diazosulfide is at Pd (pph
3)
4Do and the Suzuki linked reaction takes place under the condition of catalyzer make target compound Tr3RT, productive rate 57%.
1HNMR(CDCl
3,400MHz):δ8.56-8.59(d,3H),8.15-8.17(m,6H),8.06(s,3H),7.99-8.01(d,3H),7.90-7.92(d,3H),7.09(s,3H),3.07-3.11(m,6H),2.72-2.76(t,6H),2.25-2.32(m,6H),1.71-1.79(m,6H),1.26-1.38(m,18H),0.91-1.00(m,48H),0.61-0.72(m,27H).
13CNMR(CDCl
3,100MHz):δ154.17,154.13,153.01,146.07,144.41,140.57,139.19,138.17,135.28,132.80,129.10,127.90,127.27,126.46,125.76,124.77,123.02,121.51,56.00,37.75,31.750,31.60,30.73,30.53,29.10,22.67,22.38,14.14,13.96.
Embodiment 3:
Reaction formula
According to reaction formula, compound 1 and duplex tetramethyl ethylene ketone boric acid ester, Potassium ethanoate is at Pd (dppf)
2Cl
2Do and the Suzuki linked reaction takes place under the condition of catalyzer make compound 2.With products therefrom 2 and 4(5-bromo-4-hexyl thiophene-2-yl)-7-(4-hexyl thiophene-2-yl)-2,1, the 3-diazosulfide is at Pd (pph
3)
4Do and the Suzuki linked reaction takes place under the condition of catalyzer make target compound Tr6RT, productive rate 85%.
1HNMR(CDCl
3,400MHz):δ8.44-8.46(d,3H),8.10(s,3H),8.02(s,3H),7.87-7.93(m,6H),7.61-7.64(t,6H),7.06(s,3H),3.02-3.09(m,6H),2.87-2.91(t,6H),2.70-2.74(t,6H),2.15-2.19(m,6H),1.80-1.84(m,6H),1.71-1.74(t,6H),1.57(s,6H),1.26-1.44(m,36H),0.91-1.01(m,46H),0.63-0.67(m,32H).
13CNMR(CDCl
3,100MHz):δ153.93,152.74,152.71,145.45,144.42,140.23,139.90,139.71,139.10,138.13,137.09,132.56,130.52,129.01,127.36,127.34,125.96,125.90,125.65,125.24,124.78,124.75,122.72,121.56,55.83,37.10,31.94,31.77,31.74,31.56,31.20,30.70,30.51,29.71,29.67,29.55,29.44,29.38,29.35,29.08,24.04,22.70,22.66,22.33,24.15,22.70,22.62,22.37,14.14,13.96.
Embodiment 4:
Device architecture as the organic electroluminescence device of luminescent layer:
A kind of ruddiness device A, device architecture is: ITO/PEDOT:PSS(50nm)/Tr2RT(82nm)/TPBi(30nm)/LiF(1.3nm)/Al(80nm); Wherein Tr2RT is three and the multi-arm structure thiophene derivant red light material of indenes, as luminescent layer, and prepares for spin-coating method.
Embodiment 5:
Fabricate devices structure as the organic electroluminescence device of luminescent layer:
A kind of ruddiness device B, device architecture is: ITO/PEDOT:PSS (50nm)/Tr3RT (82nm)/TPBi (30nm)/LiF (1.3nm)/Al (80nm); Wherein Tr3RT is three and the multi-arm structural derivative of indenes-thiophene, as luminescent layer, and prepares for spin-coating method.
Embodiment 6:
Fabricate devices structure as the organic electroluminescence device of luminescent layer:
A kind of ruddiness device C, device architecture is: ITO/PEDOT:PSS (25nm)/Tr6RT (74nm)/TPBi(25nm)/LiF (1nm)/Al (100nm); Wherein Tr6RT is three and the multi-arm structure thiophene derivant ruddiness material of indenes, as luminescent layer, and prepares for spin-coating method.
Although we are in conjunction with exemplary embodiment, the present invention has been described particularly, but it will be appreciated by those skilled in the art that under the situation that does not break away from the spirit and scope of the present invention that the aforesaid right requirement limits, can make various modifications and change in form and details.
Claims (3)
1. red light material, it is characterized in that this material with three and indenes be nuclear, be the polysubstitution compound composition star-type multi-arm structured material of an arm with thiophene-benzene thiazole derivative that its formula is as shown in the formula shown in the I:
In the general formula I, X is thiophene derivant, its array structure specific as follows:
Wherein, R is C
1-C
12Alkyl, C
1-C
12Alkoxyl group; N is nitrogen-atoms, and S is sulphur atom.
2. red light material is characterized in that this material is the star-type multi-arm structured material, has the structure as general formula I I:
Among the general formula I I, X is thiophene derivant, its array structure specific as follows:
Wherein, R is C
1-C
12Alkyl, C
1-C
12Alkoxyl group; N is nitrogen-atoms, and S is sulphur atom.
3. the application of a red light material as claimed in claim 1 or 2, it is characterized in that this material is applied to organic electroluminescence device, device architecture is anode/hole transmission layer/luminescent layer/electron transfer layer/negative electrode, and wherein the star-type multi-arm structured material is as luminescent layer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555318A (en) * | 2013-10-21 | 2014-02-05 | 南京邮电大学 | Red light material and preparation method and applications thereof |
| CN107353891A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application |
| CN107602551A (en) * | 2017-09-26 | 2018-01-19 | 四川大学 | A kind of preparation method and applications of the star-like non-fullerene small molecule receptor of broad-band gap |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333439A (en) * | 2008-06-27 | 2008-12-31 | 南京邮电大学 | Organic photoelectric functional material based on trisubstituted triindene structure unit and uses thereof |
| CN102807534A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic semiconductor material and preparation method thereof |
-
2013
- 2013-04-22 CN CN2013101419836A patent/CN103289676A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333439A (en) * | 2008-06-27 | 2008-12-31 | 南京邮电大学 | Organic photoelectric functional material based on trisubstituted triindene structure unit and uses thereof |
| CN102807534A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic semiconductor material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIN-LIANG WANG ET AL.: "Solution-Processable Gradient Red-Emitting π-Conjugated Dendrimers Based on Benzothiadiazole as Core: Synthesis, Characterization, and Device Performances", 《J. ORG. CHEM.》, vol. 74, no. 19, 10 September 2009 (2009-09-10), pages 7449 - 7456 * |
| 乔智等: "电致红光聚合物材料的研究进展", 《高分子材料科学与工程》, vol. 25, no. 1, 31 January 2009 (2009-01-31), pages 161 - 164 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555318A (en) * | 2013-10-21 | 2014-02-05 | 南京邮电大学 | Red light material and preparation method and applications thereof |
| CN107353891A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application |
| CN107602551A (en) * | 2017-09-26 | 2018-01-19 | 四川大学 | A kind of preparation method and applications of the star-like non-fullerene small molecule receptor of broad-band gap |
| CN107602551B (en) * | 2017-09-26 | 2020-03-03 | 四川大学 | Preparation method and application of wide-band-gap star-shaped non-fullerene small-molecule receptor |
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Application publication date: 20130911 |