CN104745176A - Aggregation-induced emissive blue-ray molecule by construction of dibenzothiophene sulfone unit as well as preparation method and application of aggregation-induced emissive blue-ray molecule - Google Patents
Aggregation-induced emissive blue-ray molecule by construction of dibenzothiophene sulfone unit as well as preparation method and application of aggregation-induced emissive blue-ray molecule Download PDFInfo
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Abstract
The invention discloses an aggregation-induced emissive blue-ray molecule by construction of dibenzothiophene sulfone unit as well as a preparation method and application of the aggregation-induced emissive blue-ray molecule. Starting from 3,7-di-brominated dibenzothiophene sulfone, tetraphenyl ethylene units with different replace sites are introduced by means of a one-step Suzuki reaction to finally obtain the target compound. Controllable adjustment of emission colors can be realized by fine control of the structure and adopting different connecting sites and the method for adjusting conjugated degree. The aggregation-induced emissive blue-ray molecule has excellent thermal stability, has relatively high solid-state fluorescence quantum yield and blue-ray emission, and can be used as a blue-ray organic emissive diode luminescent layer material. In the blue-ray molecule, the blue-green light emission color has the coordinates of (0.19, 0.36) and current efficiency of 8.7cd/A, and the blue light emission color has coordinates of (0.17, 0.28) and current efficiency of 6.2cd/A.
Description
Technical field
The present invention relates to a kind of dibenzothiophene sulphone unit and construct aggregation-induced emission blue light molecule and preparation method thereof and the purposes as blue light organic emissive LED lighting layer material.
Background technology
Last century the eighties Kodak the people such as doctor Deng Qingyun invention multilayered structure first Organic Light Emitting Diode since, the research work of high efficiency organic electroluminescence material just enters brand-new epoch.In order to realize full-color display and solid-state illumination, efficient, that stable, purity of color is high ruddiness, green glow and blue light material are indispensable.Through the development of two more than ten years, ruddiness and green light material can meet business-like demand, but the blue light material of excellent performance is still rare, because the larger energy gap that has of blue light emitting material is disadvantageous for current carrier to the injection of luminescent layer and transmission.Therefore, how to obtain high-performance, the blue light material of high color purity become current electroluminescent organic material research emphasis.Although more existing blue light materials appear in the newspapers, the dark blue luminescent material of efficient stable is still very rare.Luminescent material is present in electroluminescent device with the form of thin-film state, and the fluorescent material of the overwhelming majority also exists the problem of " aggregation inducing fluorescent quenching " (ACQ) and spectral red shift because intramolecular π-π interacts.Calendar year 2001, this loyal academician seminar Late Cambrian of Tang also reports the compound that a class has aggregation-induced emission (AIE) character, and the luminescence when solution state of this compounds is very weak or not luminous, and when solid-state, have high fluorescence quantum yield.The luminescent behavior of this " abnormality " causes great interest and the extensive concern of people.
Some compounds with aggregation-induced emission (AIE) character are in the news out in succession, and are applied in OLED.This seminar adopts the method regulating different connection site and change conjugated degree in work before, obtains a series of blue light emitting material.But the molecule of not all employing the method synthesis all has High Efficiency Luminescence performance.Be intended for synthesizing aggregation-induced emission molecule further and guidance is provided, need to probe into more polymolecular internal factor (mobility, energy gap etc.).Consider that this typical AIE molecule of tetraphenyl ethylene is based on hole transport performance, for improving its electronic transmission performance to obtaining more high efficiency light emitting molecule, we introduce this electric transmission unit of dibenzothiophene sulphone, and combine the method regulating different connection site and change conjugated degree, obtain three aggregation-induced emission molecules containing dibenzothiophene sulphone unit.
Summary of the invention
The object of the invention is to introduce electric transmission unit in aggregation-induced emission molecule, there is provided a class dibenzothiophene sulphone unit to construct aggregation-induced emission blue light molecule and preparation method thereof and be used as the purposes of blue light organic emissive LED lighting layer, this compounds has good thermostability and higher luminous efficiency.
The technical scheme realizing the object of the invention is specific as follows:
A kind of dibenzothiophene sulphone unit constructs aggregation-induced emission blue light molecule, has formula (I), formula II or the structure shown in formula III:
A kind ofly prepare the method that above-mentioned dibenzothiophene sulphone unit constructs aggregation-induced emission blue light molecule, comprise the following steps: under shielding gas atmosphere, 3 are added in Schlenk pipe, 7-dibromo dibenzothiophene sulphone (DBTS-2Br), boric acid compound, alkali and palladium catalyst, wherein, the mol ratio of 3,7-dibromo dibenzothiophene sulphone, boric acid compound, alkali is 1:4:20; Then add toluene/ethanol/water mixed solvent that volume ratio is 4:1:2, be stirred to abundant reaction in 90-100 DEG C, namely obtain dibenzothiophene sulphone unit according to claim 1 and construct aggregation-induced emission blue light molecule; Described boric acid compound is
Described shielding gas is nitrogen, and described water is deoxidized water.
Described alkali is sodium carbonate or salt of wormwood.
Described palladium catalyst is tetra-triphenylphosphine palladium.
This preparation method is further comprising the steps of: the thick product of aggregation-induced emission blue light molecule obtained is carried out preliminary separation and purification by silica gel chromatography column chromatography.
Described silica gel chromatography column chromatography eluent used is the sherwood oil/trichloromethane mixing solutions of volume ratio 1:1.
Dibenzothiophene sulphone unit prepared by the present invention constructs the application of aggregation-induced emission blue light molecule as blue light material.
Dibenzothiophene sulphone unit prepared by the present invention constructs aggregation-induced emission blue light molecule can be used as blue light organic emissive LED lighting layer material.
The present invention sets out from 3,7-dibromo dibenzothiophene sulphone, and by changing the method for connection site and adjustment conjugated degree, react the different tetraphenyl ethylene unit of introducing three with Suzuki, one-step synthesis obtains target compound.
Synthetic route of the present invention is as follows:
The present invention has the following advantages and beneficial effect:
(1) the present invention constructs the aggregation-induced emission molecule containing dibenzothiophene sulphone first.
(2) by the precise controlling of structure, adopt the method for different connection site and adjustment conjugated degree, achieve the controllable adjustment of glow color.
(3) compound of the present invention can be used as organic light-emitting diode layer material, and organic light emitting diode device demonstrates blue green light or blue emission.Wherein, blue green light is launched chromaticity coordinates and is positioned at (0.19,0.36), and current efficiency is 8.7cd/A, and blue emission chromaticity coordinates is positioned at (0.17,0.28), and current efficiency is 6.2cd/A.
Embodiment
In order to understand content of the present invention better, below in conjunction with specific embodiment, content of the present invention is described further, but protection content of the present invention is not limited to following examples.
Raw material used in the embodiment of the present invention can be buied by market, or the synthesis of available methods known in the art obtains.
Embodiment 1
Under nitrogen atmosphere, compound 3,7-dibromo dibenzothiophene sulphone (100mg, 0.27mmol), boric acid 1 (306mg is added in Schlenk pipe, 0.67mmol), the Pd (PPh of salt of wormwood (740mg, 5.4mmol) and catalytic amount
3)
4, then add toluene (8mL), ethanol (1.5mL) and deoxidized water (3.3mL), within 24 hours, make it fully react in 90 DEG C of stirrings.After completion of the reaction, product is cooled to room temperature, with toluene extraction, collects organic phase, use anhydrous Na
2sO
4drying, obtains thick product.With sherwood oil and methylene dichloride (v/v, 2/1) for eluent, product is used silica gel chromatography column chromatography, separation and purification, vacuum-drying, obtain green solid (205mg, productive rate 87%), and use
1h NMR,
13c NMR, MS and EA characterize structure, confirm that this green solid has the structure shown in formula (I).
1h NMR (300MHz, CDCl
3) δ (ppm): 7.98 (s, 2H), 7.81 (s, 4H), 7.39 (d, J=8.1Hz, 4H), 7.06-7.13 (m, 34H).
13c NMR (100MHz, CDCl
3) δ (ppm): 144.2,143.4,143.3,143.1,141.7,140.0,138.5,136.4,132.1,131.3,129.9,127.8,127.6,126.7,126.6,126.5,126.1,121.7,120.4.MS (EI), m/z:876.18 (C
64h
44o
2s, [M
+] 876.31) .C
64h
44o
2s ultimate analysis calculated value: C, 87.64; H, 5.06; S, 3.66.Actual measured value: C, 87.39; H, 5.22; S, 3.64.
Embodiment 2
Under nitrogen atmosphere, compound 3,7-dibromo dibenzothiophene sulphone (100mg, 0.27mmol), boric acid 2 (315mg is added in Schlenk pipe, 0.67mmol), the Pd (PPh of salt of wormwood (740mg, 5.4mmol) and catalytic amount
3)
4, then add toluene (8mL), ethanol (1.5mL) and deoxidized water (3.3mL), within 24 hours, make it fully react in 90 DEG C of stirrings.After completion of the reaction, product is cooled to room temperature, with toluene extraction, collects organic phase, use anhydrous Na
2sO
4drying, obtains thick product.With sherwood oil and methylene dichloride (v/v, 2/1) for eluent, product is used silica gel chromatography column chromatography, separation and purification, vacuum-drying, obtain pale green powder (183mg, productive rate 75%), and use
1h NMR,
13c NMR, MS and EA characterize structure, confirm that this pale green powder has the structure shown in formula II.
1h NMR (300MHz, CDCl
3) δ (ppm): 7.82 (d, J=8.4Hz, 2H), 7.75 (s, 2H), 7.59 (d, J=7.8Hz, 2H), 7.10-7.14 (m, 30H), 6.91-7.00 (m, 6H), 2.11 (s, 6H).
13c NMR (100MHz, CDCl
3) δ (ppm): 144.2,143.7,143.5,143.4,141.4,140.2,137.8,137.4,134.8,134.2,133.6,131.3,131.2,129.8,129.2,128.8,127.7,127.6,126.6,126.5,126.4,122.8,121.1,20.3.MS (EI), m/z:904.34 (C
66h
48o
2s, [M
+] 904.34) .C
66h
48o
2s ultimate analysis calculated value: C, 87.58; H, 5.35; S, 3.54.Actual measured value: C, 87.34; H, 5.50; S, 3.53.
Embodiment 3
Under nitrogen atmosphere, compound 3,7-dibromo dibenzothiophene sulphone (100mg, 0.27mmol), boric acid 3 (306mg is added in Schlenk pipe, 0.67mmol), the Pd (PPh of salt of wormwood (740mg, 5.4mmol) and catalytic amount
3)
4, then add toluene (8mL), ethanol (1.5mL) and deoxidized water (3.3mL), within 24 hours, make it fully react in 90 DEG C of stirrings.After completion of the reaction, product is cooled to room temperature, with toluene extraction, collects organic phase, use anhydrous Na
2sO
4drying, obtains thick product.With sherwood oil and methylene dichloride (v/v, 2/1) for eluent, product is used silica gel chromatography column chromatography, separation and purification, vacuum-drying, obtain white powder (194mg, productive rate 82%), and use
1h NMR,
13c NMR, MS and EA characterize structure, confirm that this white powder has the structure shown in formula III.
1h NMR (300MHz, CDCl
3) δ (ppm): 7.72 (d, J=8.1Hz, 2H), 7.52 (s, 2H), 7.47 (d, J=7.8Hz, 2H), 7.22-7.24 (m, 8H), 7.05-7.13 (m, 26H).
13c NMR (100MHz, CDCl
3) δ (ppm): 144.3,143.7,143.5,143.3,143.1,141.8,140.2,138.4,138.0,132.3,131.3,131.2,130.6,129.9,128.4,128.0,127.8,127.7,126.9,126.6,126.5,124.9,121.5,120.8.MS (EI), m/z:876.13 (C
64h
44o
2s, [M
+] 876.31) .C
64h
44o
2s ultimate analysis calculated value: C, 87.64; H, 5.06; S, 3.66.Actual measured value: C, 87.71; H, 5.19; S, 3.62.
After collecting organic phase in the embodiment of the present invention, be use anhydrous Na
2sO
4drying, also can adopt other siccative, as long as the moisture that can remove in organic phase and not reacting with organic phase.
Compound of the present invention is used as the emitting layer material of blue light organic emissive diode.The device current recorded using light emitting molecule I of the present invention as emitting layer material is most effective reaches 8.7cd/A, and the chromaticity coordinates of its correspondence is (0.19,0.36).Light emitting molecule II is positioned at (0.17,0.28) as the blue emission chromaticity coordinates of luminescent layer, and current efficiency is 6.2cd/A.
Claims (10)
1. dibenzothiophene sulphone unit constructs an aggregation-induced emission blue light molecule, it is characterized in that, has formula (I), formula II or the structure shown in formula III:
2. prepare the method that dibenzothiophene sulphone unit according to claim 1 constructs aggregation-induced emission blue light molecule for one kind, it is characterized in that, comprise the following steps: under shielding gas atmosphere, 3 are added in Schlenk pipe, 7-dibromo dibenzothiophene sulphone, boric acid compound, alkali and palladium catalyst, wherein, the mol ratio of 3,7-dibromo dibenzothiophene sulphone, boric acid compound, alkali is 1:4:20; Then add toluene/ethanol/water mixed solvent that volume ratio is 4:1:2, be stirred to abundant reaction in 90-100 DEG C, namely obtain dibenzothiophene sulphone unit according to claim 1 and construct aggregation-induced emission blue light molecule; Described boric acid compound is
3. dibenzothiophene sulphone unit according to claim 2 constructs the preparation method of aggregation-induced emission blue light molecule, it is characterized in that: described shielding gas is nitrogen.
4. dibenzothiophene sulphone unit according to claim 2 constructs the preparation method of aggregation-induced emission blue light molecule, it is characterized in that: described water is deoxidized water.
5. dibenzothiophene sulphone unit according to claim 2 constructs the preparation method of aggregation-induced emission blue light molecule, it is characterized in that: described alkali is sodium carbonate or salt of wormwood.
6. dibenzothiophene sulphone unit according to claim 2 constructs the preparation method of aggregation-induced emission blue light molecule, it is characterized in that: described palladium catalyst is tetra-triphenylphosphine palladium.
7. the dibenzothiophene sulphone unit according to any one of claim 2-6 constructs the preparation method of aggregation-induced emission blue light molecule, characterized by further comprising following steps: the thick product of aggregation-induced emission blue light molecule obtained is carried out preliminary separation and purification by silica gel chromatography column chromatography.
8. the preparation method constructing aggregation-induced emission blue light molecule based on dibenzothiophene sulphone unit according to claim 7, is characterized in that: described silica gel chromatography column chromatography eluent used is the sherwood oil/trichloromethane mixing solutions of volume ratio 1:1.
9. dibenzothiophene sulphone unit according to claim 1 constructs the application of aggregation-induced emission blue light molecule as blue light material.
10. dibenzothiophene sulphone unit according to claim 1 constructs the application of aggregation-induced emission blue light molecule as blue light organic emissive LED lighting layer material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478458A (en) * | 2015-08-31 | 2017-03-08 | 香港科技大学深圳研究院 | Schiff base compound based on tetraphenylethylene and Maleic nitrile and its preparation method and application |
| CN108822074A (en) * | 2018-06-28 | 2018-11-16 | 华中师范大学 | A kind of di-thiofuran ethylene compound and its preparation method and application with tetraphenyl ethylene unit |
| CN109293254A (en) * | 2018-11-06 | 2019-02-01 | 盐城易快来科技有限公司 | A kind of enhanced mobile phone display screen of hardness |
| CN111875636A (en) * | 2020-08-05 | 2020-11-03 | 西北工业大学 | Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof |
| CN114957309A (en) * | 2022-04-11 | 2022-08-30 | 同济大学 | Sulfuryl-modified silico-fluorene and dithiophene-sulfone-sila-fluorene derivatives, and preparation method and application thereof |
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| CN102850320A (en) * | 2011-06-28 | 2013-01-02 | 海洋王照明科技股份有限公司 | Compound containing dibenzothiophene sulfone and preparation method and application thereof |
| CN103396285A (en) * | 2013-08-19 | 2013-11-20 | 武汉大学 | Compound containing tetraphenyl ethylene unit, preparation method and applications thereof |
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2015
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Patent Citations (2)
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| CN102850320A (en) * | 2011-06-28 | 2013-01-02 | 海洋王照明科技股份有限公司 | Compound containing dibenzothiophene sulfone and preparation method and application thereof |
| CN103396285A (en) * | 2013-08-19 | 2013-11-20 | 武汉大学 | Compound containing tetraphenyl ethylene unit, preparation method and applications thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478458A (en) * | 2015-08-31 | 2017-03-08 | 香港科技大学深圳研究院 | Schiff base compound based on tetraphenylethylene and Maleic nitrile and its preparation method and application |
| CN106478458B (en) * | 2015-08-31 | 2018-08-03 | 香港科技大学深圳研究院 | Schiff base compound and its preparation method and application based on tetraphenylethylene and Maleic nitrile |
| CN108822074A (en) * | 2018-06-28 | 2018-11-16 | 华中师范大学 | A kind of di-thiofuran ethylene compound and its preparation method and application with tetraphenyl ethylene unit |
| CN108822074B (en) * | 2018-06-28 | 2020-07-17 | 华中师范大学 | Dithiophene ethylene compound with tetraphenylethylene unit and preparation method and application thereof |
| CN109293254A (en) * | 2018-11-06 | 2019-02-01 | 盐城易快来科技有限公司 | A kind of enhanced mobile phone display screen of hardness |
| CN111875636A (en) * | 2020-08-05 | 2020-11-03 | 西北工业大学 | Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof |
| CN111875636B (en) * | 2020-08-05 | 2023-03-31 | 西北工业大学 | Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof |
| CN114957309A (en) * | 2022-04-11 | 2022-08-30 | 同济大学 | Sulfuryl-modified silico-fluorene and dithiophene-sulfone-sila-fluorene derivatives, and preparation method and application thereof |
| CN114957309B (en) * | 2022-04-11 | 2024-02-23 | 同济大学 | Sulfonyl modified silafluorene and dithiophene sulfonyl silafluorene derivative as well as preparation method and application thereof |
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